JP2003096011A - Aralkylated biphenol, and its production method and application - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an aralkylated biphenol that is useful as a curing agent for a sealing agent of an epoxy resin-based semiconductor and can form an epoxy resin composition of low water absorption capacity, low elastic modulus and low melt viscosity, its efficient production method and its application as the curing agent for the epoxy resin. SOLUTION: The aralkylated biphenol where 1 to 3 on average aralkyl groups such as a benzyl group per one molecule of 4,4'-dihydroxybiphenyl are bonded to its aromatic ring is used as the curing agent for the epoxy resin.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to an alalkylated biphenol useful as a molding material, various binders, coating materials, laminating materials, etc., a method for producing the same, and an epoxy resin composition using the same as an epoxy resin curing agent or a composition thereof. Regarding cured products. Particularly useful as a curing agent in epoxy resin-based semiconductor encapsulants, low water absorption, low elastic modulus,
The present invention relates to an alalkylated biphenol having a low melt viscosity.

[0002]

2. Description of the Related Art As a semiconductor encapsulation method, resin encapsulation with an epoxy resin is generally used from the viewpoint of economical efficiency, productivity and physical properties. Among them, orthocresol novolac type epoxy resin and phenol novolac curing agent are used. Resin encapsulations consisting of and an inorganic filler such as silica have been widely used. However, in recent years, the required performance of the encapsulant has changed significantly with the increase in the size of the LSI chip, the thinner / smaller package, and the change in the mounting method. It is becoming difficult to adequately respond in terms of heat resistance and reliability. For example, during heat treatment during soldering, cracking or peeling of the package due to rapid vaporization and expansion of moisture absorption becomes a problem.

Therefore, it is desired to develop an epoxy resin or a curing agent which has a low hygroscopic property and a low elastic modulus at the soldering temperature. In response to such a demand, a method using a phenol aralkyl resin (Japanese Patent Publication No. 47-13782, Japanese Patent Publication No. 47-15111, etc.) as a curing agent has been put into practical use. Phenol aralkyl resin is obtained by reacting a phenol compound with an aromatic compound having two halomethyl groups, alkoxymethyl groups, hydroxymethyl groups, etc., and has the effect of lowering the OH group concentration, resulting in low water absorption and heat. It was intended to lower the elasticity, and some effects were recognized, but it was not yet sufficient.

Recently, a phenol biphenyl aralkyl resin of a type using bis (methoxymethyl biphenyl) as an aromatic compound having two or more alkoxymethyl groups has been proposed (Japanese Patent No. 3122834 etc.), and some improvement has been made. However, even in this case, it cannot be said to be sufficiently satisfactory. In particular, in the situation where the soldering temperature rise is inevitable for lead-free soldering, materials with lower viscosity, lower elastic modulus and lower water absorption were required.

Under these circumstances, it has been proposed to use polycyclic aromatic compounds such as naphthol (Japanese Patent Laid-Open No. 9-176262), but it is possible to use phenol excessively in order to increase the melt viscosity. It is indispensable and is not necessarily a sufficient improvement.

In addition to these, naphthol aralkyl resin and petroleum pitch copolymerized with formaldehyde together with phenol, addition reaction product of divinylbenzene and phenol, addition reaction product of dicyclopentadiene and phenol, etc. are proposed. It has not reached the point of satisfying the characteristics.

Further, benzylated products of specific polyphenols have also been proposed (JP-A-8-120039).
No.), it is disclosed that an epoxy resin composition having a low melt viscosity and being excellent in heat resistance, low water absorption, mechanical strength and the like can be obtained by mixing with an epoxy resin, but it is said to be particularly preferable. The benzylated polyphenols in which the phenol skeleton is linked by a methylene group or a thioether group are insufficient in low elastic modulus and are not satisfactory as a lead-free solder compatible material. Further, in this proposal, it is described that the melt viscosity is hardly changed by the benzylation, so that it is understood that the polyphenols as the benzylation raw material are focused on those having a low melt viscosity. However, as the raw material polyphenols, those represented by the general formula are wide-ranging, and in fact, the viscosity is too high, and thus those which do not meet the above description are also included. For example, in this general formula, X
Indicates a direct bond, and those in which n is 1 or more have a high viscosity and are expensive, and therefore, considering the above description together, practical appeal is not felt.

[0008]

Under the above circumstances, the present inventors have found that when used as a curing agent in an epoxy resin curing system for semiconductor encapsulation, it has low melt viscosity, low water absorption and low elasticity. The investigation was carried out in search of materials that can achieve high efficiency. As a result, it cannot be used as an epoxy resin curing agent due to its high melting point, and the above-mentioned JP-A-8-120039.
When 4,4'-dihydroxybiphenyl, which is difficult to be considered as a raw material in No. 1, is used as an epoxy resin curing agent when it is alalkylated at a predetermined ratio, it has a low melt viscosity, low water absorption and low elastic modulus. The present invention has been reached by finding that an alkylated product capable of forming a resin composition is obtained.

Therefore, an object of the present invention is to provide an alalkylated biphenol which can achieve low melt viscosity, low water absorption and low elasticity when used as a curing agent in a semiconductor encapsulating epoxy resin curing system. Especially.
Another object of the present invention is to provide a method for efficiently producing such an alkylated biphenol.
Still another object of the present invention is to provide the use of such an alkylated biphenol as an epoxy resin curing agent, and a curable composition blended with an epoxy resin and a cured product thereof.

[0010]

That is, the present invention is as follows.
An average of 1 aralkyl group represented by the general formula (1) is contained in the aromatic ring per 4′-dihydroxybiphenyl molecule.
It is an alalkylated biphenol which is bound in a ratio of 3 to 3.

[Chemical 3] (In the formula, Ar is an aryl group, R ¹ and R ² are hydrogen or a methyl group)

The present invention also provides a method for producing an alalkylated biphenol, which comprises reacting 4,4'-dihydroxybiphenyl with an alalkylating agent represented by the general formula (2) in the presence of a soluble solvent. is there.

[Chemical 4] (Wherein Ar is an aryl group, R ¹ and R ² are hydrogen or a methyl group, X is a halogen, a hydroxyl group or an alkoxy group) This reaction is preferably carried out in the presence of an acid catalyst.

The present invention also relates to an epoxy resin curing agent comprising the above alkylated biphenol, an epoxy resin composition containing the epoxy resin and the above alkylated biphenol, and an epoxy resin cured product obtained by curing the same.

[0013]

BEST MODE FOR CARRYING OUT THE INVENTION The alalkylated biphenol of the present invention has the formula (3), preferably 1.3 to 2.8 on average per molecule of 4,4′-dihydroxybiphenyl. The aralkyl group represented by 1) is 4,4 '.
-A compound that is bonded to the aromatic ring of dihydroxybiphenyl and may be a single compound, but as long as the average number is within the above range, two or more kinds having different numbers and / or bonding positions of aralkyl groups. It may be a mixture of the above compounds. Generally, a mixture of two or more kinds is preferable because the melt viscosity can be lowered.

In the above general formula (1), Ar is an aryl group such as phenyl, naphthyl, biphenyl,
Examples thereof include groups such as methylphenyl, benzylphenyl, and methylnaphthyl, with preference given to phenyl. R ¹ and R ² are each hydrogen or a methyl group, and preferably both are hydrogen.

The alkylated biphenols of the present invention are
A mixture of two or more kinds of alalkylated biphenols in which about 1 to 8, preferably about 1 to 5 aralkyl groups are bonded per molecule of 4,4′-dihydroxybiphenyl is preferable. Specific examples of such alalkylated biphenols include the following (3) to (8)
It is conceivable that one or a mixture of two or more (mono-penta) aralkylated biphenols as shown in (4) and the average number of aralkyl groups is within a predetermined range. That is, the aralkyl group is generally directly bonded to the aromatic ring of 4,4′-dihydroxybiphenyl, as in the alalkylated biphenols represented by the formulas (3) to (7), Like the alalkylated biphenol represented by the formula (8), a part thereof is bonded to the aryl group of the alalkyl group directly bonded to the aromatic ring to form an aromatic ring of 4,4′-dihydroxybiphenyl. May be indirectly bound to.

[0016]

[Chemical 5]

[0017]

[Chemical 6]

[0018]

[Chemical 7]

[0019]

[Chemical 8]

[0020]

[Chemical 9]

[0021]

[Chemical 10]

Such alalkylated biphenols can be analyzed by mass spectrum analysis (MS), proton NMR (H
-NMR), gel permeation chromatography (GPC),
It can be identified by the hydroxyl equivalent. FIG. 1 is a mass spectrum chart of the benzylated biphenol in which the aralkyl group obtained in Example 1 is a benzyl group. Table 1 shows the relationship between the molecular weight peak of the mass spectrum and the number of benzyl groups bonded to the aromatic ring of 4,4′-dihydroxybiphenyl.

[0023]

[Table 1]

FIG. 2 is a proton NMR chart of the above-mentioned benzylated biphenol. The aromatic (biphenol-derived and benzyl group-derived) is 6.5 to 7.6 ppm, and the benzyl group-derived methylene is 3.6 to 4.1 ppm. , OH groups were detected at 9.2 to 9.5 ppm, and it was found that the structure was such that biphenol was substituted with benzyl group.

FIG. 3 shows GP of the above-mentioned benzylated biphenol.
It is a C chart, and retention time 31.197 is biphenol and has a peak distribution in high molecular weight according to the substitution number of a benzyl group.

Further, the hydroxyl equivalent of 191 g / eq, which is obtained by acetylating the OH group of benzylated biphenol with excess acetic anhydride and quantifying the acetic anhydride consumed at that time, is 4,4'-dihydroxybiphenyl. The value is the same as the value obtained by substituting 2.2 benzyl groups in one molecule.

From the above, the above benzylated biphenol is a mixture of 4,4'-dihydroxybiphenyl having 1 to 5 benzyl groups substituted on the aromatic ring, and the number of substitutions is an average per biphenol molecule. 2.2
It turns out that it is an individual.

4,4'-dihydroxybiphenyl, which is a raw material of the alalkylated biphenol, has a high melting point and is not compatible with the epoxy resin by itself, so that it is not an excellent curing agent, but it is alkylated. The alalkylated biphenol of the present invention has excellent compatibility with an epoxy resin, and can form an epoxy resin composition having a low melt viscosity, low water absorption, and a low elastic modulus when heated.
In the alkylated biphenol of the present invention, if the number of benzyl groups is less than the above range, the desired effect as an epoxy resin curing agent cannot be sufficiently exhibited, and if the number is more than the above range, the epoxy resin curing agent is cured. When used as an agent, the curing rate cannot be said to be sufficiently high, and neither is preferable.

The alalkylated biphenols of the present invention are
It can be obtained by alkylating 4,4′-dihydroxybiphenyl with an alkylating agent represented by the general formula (2). In the general formula (2), Ar is an aryl group, and examples thereof include phenyl, naphthyl, biphenyl, methylphenyl, benzylphenyl and methylnaphthyl groups. In addition, R ¹ and R ²
Are each hydrogen or a methyl group, and preferably both are hydrogen. X is a halogen, a hydroxyl group or an alkoxy group.

When X is halogen such as Cl, Br, I, that is, when the one represented by the general formula (2) is an aralkyl halide, specifically, benzyl chloride,
Benzyl bromide, benzyl iodide, o-methylbenzyl chloride, m-methylbenzyl chloride, p-methylbenzyl chloride, p-ethylbenzyl chloride, p-isopropylbenzyl chloride,
p-t-butylbenzyl chloride, p-cyclohexylbenzyl chloride, p-phenylbenzyl chloride, 2-naphthylmethyl chloride, 7-methyl-2-
Naphthylmethyl chloride and their nuclear substitution isomers,
Examples thereof include α-methylbenzyl chloride and α, α-dimethylbenzyl chloride.

When X is a hydroxyl group, that is, the general formula (2)
When the compound represented by is an alkylalkyl hydroxide, specifically, benzyl alcohol, o-methylbenzyl alcohol, m-methylbenzyl alcohol, p-methylbenzyl alcohol, p-ethylbenzyl alcohol, p-isopropylbenzyl alcohol, p -T-butylbenzyl alcohol, p-cyclohexylbenzyl alcohol, p-phenylbenzyl alcohol, 2-naphthylcarbinol, 7-methyl-2-naphthylcarbinol and their nuclear substitution isomers, α-methylbenzyl alcohol, α, Examples include α-dimethylbenzyl alcohol.

When X is an alkoxide in the general formula (2), it is preferably an alkoxide having 1 to 4 carbon atoms, for example, methoxide, ethoxide, isopropoxide, n-propoxide, isobutyroxide, n-butyroxide, t-butoxide. It is an alkoxide such as butyroxide. Specific examples of such alalkyl alkoxides include benzyl methyl ether, o-methyl benzyl methyl ether, m-methyl benzyl methyl ether, p-methyl benzyl methyl ether, p-ethyl benzyl methyl ether, and nuclear substitutions thereof. Isomer, benzyl ethyl ether, benzyl isopropyl ether,
Examples thereof include benzyl n-propyl ether, benzyl isobutyl ether, benzyl n-butyl ether, p-methylbenzyl methyl ether, and nuclear substitution isomers thereof.

The alkylation reaction generally comprises 4,
It can be obtained by dissolving 4′-dihydroxybiphenyl in a soluble solvent and reacting with the above alkylating agent. Examples of the soluble solvent include ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dipropyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether. Ethylene glycol or diethylene glycol mono- or diethers such as diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, diethylene glycol monobutyl ether, aprotic polar such as dimethylformamide or dimethyl sulfoxide It can be mentioned medium, chlorobenzene, nitrobenzene and the like. By using such a soluble solvent, the alalkylated biphenol can be stably obtained.

The alkylation reaction is preferably carried out in the presence of an acid catalyst. Acid catalysts that can be used vary depending on the type of alkylating agent, but phosphoric acid, sulfuric acid,
Inorganic acids such as hydrochloric acid, organic acids such as oxalic acid, benzene sulfonic acid, toluene sulfonic acid, methane sulfonic acid, fluoromethane sulfonic acid, aluminum chloride, zinc chloride, stannic chloride, ferric chloride, diethyl sulphate, etc. The Del Crafts catalyst can be used alone or in combination.

The alkylation reaction is preferably carried out under conditions which form a homogeneous solution, and the soluble solvent is, for example, 1 part by weight per 4,4'-dihydroxybiphenyl.
It is preferable to use about 10 to 10 parts by weight, preferably about 2 to 8 parts by weight. Further, the acid catalyst, the kind and the substrate concentration of the solvent to be used, it is sufficient to select the kind and the amount to be used according to the target alkylation rate, etc.
0.1 mol / mol of 4,4′-dihydroxybiphenyl.
05 to 2 mol, preferably about 0.1 to 1.5 mol, and in the case of Friedel-Crafts catalyst, 0.2 to 3 mol, preferably 0.5 to 2 mol per mol of 4,4′-dihydroxybiphenyl. It is recommended to use about a mole.

The reaction is carried out with 4,4'-dihydroxybiphenyl in a soluble solvent and 1 to 3 mol, preferably 1.3 to 2.8, per mol of 4,4'-dihydroxybiphenyl.
Dissolve the molar alkylating agent and the acid catalyst,
At a temperature of 180 ° C., preferably 80 to 160 ° C., 1
It is good to carry out by maintaining for about 10 hours.

After completion of the reaction, the acid catalyst is removed by neutralizing or decomposing it, and the desired aralkylated biphenol can be separated by general operations such as extraction and distillation. In general, the alalkylated biphenol obtained by such a method is a mixture of two or more kinds having different numbers and / or bonding positions of the alalkyl groups, and can be used as it is for various purposes. It is possible to separate each component or a mixture having a smaller number of components by further performing a fractionation operation such as distillation according to the above.

The above-mentioned alalkylated biphenol of the present invention can be used for molding materials, various binders, coating materials, laminated materials and the like. It is particularly useful as an epoxy resin curing agent, and when used as a curing agent in an epoxy resin-based semiconductor encapsulating material, an epoxy resin composition having low water absorption, low elastic modulus at heat, and low melt viscosity can be obtained.

Epoxy resins that can be used with the above-described alalkylated biphenols of the present invention include:
For example, bisphenol A type epoxy resin, bisphenol F type epoxy resin, cresol novolac type epoxy resin, phenol novolac type epoxy resin, biphenyl type epoxy resin, phenol biphenyl aralkyl type epoxy resin, epoxide of aralkyl resin by xylylene bond such as phenol and naphthol. , Dicyclopentadiene type epoxy resins, glycidyl ether type epoxy resins such as dihydroxynaphthalene type epoxy resins, glycidyl ester type epoxy resins, glycidyl amine type epoxy resins, halogenated epoxy resins, etc. having two or more epoxy groups in the molecule Resins may be mentioned. These epoxy resins may be used alone or in combination of two or more.

Upon curing the epoxy resin, it is desirable to use a curing accelerator together. As such a curing accelerator, a known curing accelerator for curing an epoxy resin with a phenol resin-based curing agent can be used. For example, a tertiary amine, a quaternary ammonium salt, an imidazole and its tetraphenylboron salt, An organic phosphine compound and its boron salt, a quaternary phosphonium salt, etc. can be mentioned. More specifically, triethylamine, triethylenediamine, benzyldimethylamine, 2,4
6-tris (dimethylaminomethyl) phenol, 1,
Tertiary amines such as 8-diazabicyclo (5,4,0) undecene-7, 2-methylimidazole, 2,4-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4- Imidazoles such as methylimidazole, organic phosphine compounds such as triphenylphosphine, tributylphosphine, tri (p-methylphenyl) phosphine, tri (nonylphenyl) phosphine, tetraphenylphosphonium tetraphenylborate, tetraphenylphosphonium tetranaphthoic acid borate, etc. Can be mentioned. Among them, organic phosphine compounds and quaternary phosphonium salts are preferably used from the viewpoint of low water absorption and reliability.

If necessary, an inorganic filler, a coupling agent, a mold release agent, a colorant, a flame retardant, a flame retardant aid, a low stress agent, etc. may be added or previously added to the epoxy resin composition of the present invention. It can be used by reacting. Also, other curing agents can be used in combination. As such another curing agent, a conventionally known phenol resin type curing agent can be mentioned. For example, a compound having two or more phenolic hydroxyl groups in one molecule, such as a phenol novolac resin, a cresol novolac resin, Japanese Patent Publication Nos. 47-13782 and 4
7-15111, JP-A-6-184258, JP-A-6-136082, JP-A-7-258364, JP3122834, and the like, and phenolaralkyl resins and phenolbiphenylaralkyl resins,
Examples thereof include phenol naphthyl aralkyl resin, naphthol aralkyl resin, triphenol methane type novolac resin, and phenol resin having a dicyclopentadiene skeleton.

Further, especially when used for semiconductor encapsulation, addition of an inorganic filler is essential. Examples of such inorganic fillers include amorphous silica, crystalline silica, alumina, glass, calcium silicate, gypsum, calcium carbonate,
Magnesite, clay, talc, mica, magnesia,
Barium sulfate and the like can be mentioned, but amorphous silica and crystalline silica are particularly preferable. Further, in order to increase the compounding amount of the filler while maintaining excellent moldability, it is preferable to use a spherical filler having a wide particle size distribution that enables fine packing.

Examples of coupling agents include vinylsilane-based, aminosilane-based, epoxysilane-based, and other silane-based coupling agents and titanium-based coupling agents, and release agents include carnauba wax, paraffin wax, and the like.
Examples include stearic acid, montanic acid, and a carboxyl group-containing polyolefin wax, and examples of the colorant include carbon black. Examples of flame retardants include halogenated epoxy resins, halogen compounds, phosphorus compounds and the like, and flame retardant aids such as antimony trioxide. Examples of low stress agents include:
Examples thereof include silicone rubber, modified nitrile rubber, modified butadiene rubber, modified silicone oil and the like.

The compounding ratio of the benzylated biphenol to the epoxy resin of the present invention is 0.5 to 1.5, particularly 0.8 to 1 in terms of the hydroxyl group / epoxy group equivalent ratio in consideration of heat resistance and mechanical properties. It is preferably in the range of 0.2. Further, even when it is used in combination with another curing agent, it is preferable that the equivalent ratio of hydroxyl group / epoxy group be the above ratio.
The curing accelerator is preferably used in the range of 0.1 to 5 parts by weight with respect to 100 parts by weight of the epoxy resin in consideration of the curing characteristics and various physical properties. Further, in the epoxy resin composition for semiconductor encapsulation, although slightly different depending on the type of the inorganic filler, considering solder heat resistance, moldability (melt viscosity, fluidity), low stress, low water absorption, etc., The inorganic filler is preferably blended in such a proportion that it accounts for 60 to 93% by weight of the entire composition.

As a general method for preparing an epoxy resin composition as a molding material, the respective raw materials in a predetermined ratio are thoroughly mixed by, for example, a mixer, then kneaded by a hot roll or a kneader, and further cooled. After solidification, a method of pulverizing to an appropriate size can be mentioned. The molding material thus obtained can be used for semiconductor encapsulation by, for example, low-pressure transfer molding. Curing of the epoxy resin composition is, for example, 100 to 2
It can be performed in a temperature range of 50 ° C.

[0046]

[Example 1] 186.0 g (1.0 mol) of 4,4'-dihydroxybiphenyl, benzyl chloride 253.
0 g (2.0 mol) and diethylene glycol dimethyl ether 744.0 g were put into a four-necked flask, mixed and dissolved, and then 267.0 g (2.0 mol) of aluminum chloride was added, followed by heating to a reaction temperature of 140 ° C. The reaction was carried out for 2 hours while maintaining.

After completion of the reaction, 400 g of water was added to deactivate the aluminum chloride, and the resulting reaction solution was cooled and separated into an oil layer and an aqueous layer. The obtained oil layer was concentrated to distill off diethylene glycol dimethyl ether. Methyl isobutyl ketone (600 g) and water (600 g) were added to the concentrate to perform extraction and separation to separate an oil layer and an aqueous layer.
It was washed twice with. After washing with water, the obtained oil layer was distilled under reduced pressure to distill off methyl isobutyl ketone to obtain 253.3 g of resinous benzylated biphenol.

This had a softening point of 66 ° C. and a melt viscosity at 150 ° C. measured by an ICI melt viscometer of 0.5 poise. The OH group equivalent determined by the acetylation back titration method was 191 g / eq. A mass spectrum chart is shown in FIG. 1, a proton NMR chart is shown in FIG. 2, and a GPC chart is shown in FIG. As described above, from these data, the benzylated biphenol obtained was
One molecule of 4'-dihydroxybiphenyl was substituted with an average of 2.2 benzyl groups.

Example 2 The amount of benzyl chloride used was 37
The procedure and conditions were the same as in Example 1 except that the amount of aluminum chloride used was 9.5 g (3.0 mol) and the amount of aluminum chloride used was 406.5 g (3.0 mol). Got The benzylated phenol obtained had a softening point of 64 ° C. and was measured with an ICI melt viscometer.
Melt viscosity at 50 ° C is 0.4 poise, hydroxyl equivalent is 22
It was 8 g / eq, and was an average of 3.0 benzyl groups bonded to one molecule of 4,4′-dihydroxybiphenyl.

[Example 3] The amount of benzyl chloride used was 18
The same procedure and conditions as in Example 1 were used except that 9.8 g (1.5 mol) and the amount of aluminum chloride used were 200.3 g (1.5 mol), and 244.0 g of resinous benzylated biphenol. Got The benzylated phenol obtained had a softening point of 70 ° C. and was measured with an ICI melt viscometer of 1
Melt viscosity at 50 ° C is 0.8 poise and hydroxyl equivalent is 16
It was 5 g / eq, and was an average of 1.6 benzyl groups bonded to one molecule of 4,4′-dihydroxybiphenyl.

Examples 4 to 6 Benzylated biphenols obtained in Examples 1 to 3, epoxy resin (ESCN-195 manufactured by Sumitomo Chemical Co., orthocresol novolac type, epoxy equivalent 195 g / eq), fused silica, tri Phenylphosphine, aminosilane coupling agent and carnauba wax were blended in the proportions shown in Table 2, thoroughly mixed, then kneaded for 3 minutes with a two-roll 85 ° C. ± 3 ° C., cooled and pulverized for molding. A composition was obtained. The molding composition was molded with a transfer molding machine at a pressure of 100 kgf / cm ² at 175 ° C. for 2 minutes and then post-cured at 180 ° C. for 6 hours to obtain a water absorption coefficient, a bending elastic modulus coefficient, and a glass transition temperature (Tg) coefficient. I got a test piece.

The physical properties of these molding materials were measured by the following methods.

(1) Water Absorption Rate The water absorption rate was measured when a disk having a 50 mm diameter × 3 mm sample shape was allowed to absorb water for 168 hours under an atmosphere of 85 ° C. and a relative humidity of 85% RH. Water absorption rate (%) = (weight increase after treatment / weight before treatment)
× 100

(2) Flexural Modulus Sample shape A strip of 80 × 10 × 4 mm was allowed to stand in an atmosphere of 260 ° C. for 10 minutes and then measured according to JIS K6911.

(3) Glass transition temperature (Tg) The linear expansion coefficient was measured by TMA, and the inflection point of the linear expansion coefficient was taken as Tg.

[Comparative Example 1] Instead of the benzylated biphenols of Examples 1 to 3, a commercially available phenol aralkyl resin (HE100C-10 manufactured by Sumikin Chemical Co., OH group equivalent: 1) was used.
A molding composition was prepared and evaluated in the same manner except that 68 g / eq) was used.

Comparative Example 2 Molding was carried out in the same manner except that a commercially available phenol novolac resin (Showa High Polymer Co., Ltd., OH group equivalent 106 g / eq) was used in place of the benzylated biphenols of Examples 1 to 3. A composition was prepared and evaluated.

[Comparative Example 3] The same as in Comparative Example 3 except that biphenol (4,4'-dihydroxybiphenyl) as a raw material of the benzylated biphenols of Examples 1 to 3 was used in place of the benzylated biphenols of Examples 1 to 3. Then, a molding composition was prepared and evaluated.

The evaluation results are shown in Table 2 together with the properties of the raw material curing agent.

[0060]

[Table 2]

[0061]

INDUSTRIAL APPLICABILITY According to the present invention, it is possible to provide an alalkylated biphenol which is useful as a molding material, various binders, coating materials, laminated materials and the like. Such an alalkylated biphenol is particularly useful as an epoxy resin curing agent, and particularly when used as a semiconductor encapsulating agent, forms an epoxy resin composition having low water absorption, low elastic modulus at heat, and low melt viscosity. can do.

[Brief description of drawings]

FIG. 1 is a mass spectrum chart of benzylated biphenol obtained in Example 1.

FIG. 2 is a proton NMR chart of the benzylated biphenol obtained in Example 1.

FIG. 3 is a GPC chart of benzylated biphenol obtained in Example 1.

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Claims (10)

[Claims] 1. An aralkylated biphenol in which an average of 1 to 3 aralkyl groups represented by the general formula (1) are bonded to the aromatic ring per molecule of 4,4′-dihydroxybiphenyl. [Chemical 1] (In the formula, Ar is an aryl group, R ¹ and R ² are hydrogen or a methyl group) 2. The aralkylated phenol according to claim 1, which is a mixture of at least two kinds having different numbers and / or bonding positions of aralkyl groups. 3. The aralkylated phenol according to claim 1, wherein the aralkyl group is a benzyl group. 4. A method for producing an alalkylated biphenol, which comprises reacting 4,4′-dihydroxybiphenyl with an alalkylating agent represented by the general formula (2) in the presence of a soluble solvent. [Chemical 2] (In the formula, Ar is an aryl group, R ¹ and R ² are hydrogen or a methyl group, and X is a halogen, a hydroxyl group or an alkoxy group.) 5. The method for producing an alalkylated biphenol according to claim 4, wherein the reaction is carried out in the presence of an acid catalyst. 6. An epoxy resin curing agent comprising the alalkylated biphenol according to claim 1. 7. An epoxy resin composition containing an epoxy resin and the alkylated biphenol according to claim 1. 8. The epoxy resin composition according to claim 7, which comprises an inorganic filler. 9. The epoxy resin composition according to claim 7, which is used for semiconductor encapsulation. 10. An epoxy resin cured product obtained by curing the epoxy resin composition according to claim 7.