JPH1143531A - Modified epoxy resin, epoxy resin composition and its cured product - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject resin having a high softening point, good workability and preservability and a low melt-viscosity by glycidylating a mixture of a specific phenol compound with 4,4'-dihydroxybiphenyl. SOLUTION: This modified epoxy resin having 60-120 deg.C softening point is obtained by reacting a mixture comprising (i) a phenol compound of the formula [X is a 1-14C hydrocarbon, etc.; (a) is 1-6; (b) is 1-5; R is H, a halogen, etc.; (n) is an average and is 1-10], [preferably 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethyl- cyclohexane, etc.], and (ii) 4,4'-dihydroxybiphenyl and having <=0.4, preferably 0,05-0.25 mixing weight ratio (ii/i), with 0.5-10 mole, preferably 1.0-6.0 mole of an epihalohydrin (e.g. epichlorohydrin, etc.), based on 1 mole equivalent of hydroxyl groups of the above mixture in the presence of an alkali metal hydroxide (e.g. sodium hydroxide) at 20-120 deg.C for 5-10 hours.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to insulating materials for electric and electronic parts including sealing semiconductors, and various composite materials including laminated boards (printed wiring boards) and CFRP (carbon fiber reinforced plastic). The present invention relates to a modified epoxy resin, an epoxy resin composition, and a cured product thereof useful for an adhesive, a paint and the like.

[0002]

2. Description of the Related Art Epoxy resins are used in the fields of electric and electronic parts, structural materials, adhesives, paints, etc. due to workability and excellent electrical properties, heat resistance, adhesiveness, moisture resistance (water resistance), etc. of the cured product. Widely used in

[0003]

However, in recent years, in the field of electric and electronic devices, with rapid development, heat resistance, moisture resistance, adhesion, low viscosity for high filling of fillers, etc. Further improvement of various characteristics is required. On the other hand, it is desired to be solid at room temperature in order to improve workability. In addition, structural materials include aerospace materials,
In addition to being lightweight and having excellent mechanical properties for leisure and sports equipment applications, low viscosity resins are also required to improve workability. Many proposals have been made for epoxy resin compositions to meet these requirements, but they have not been satisfactory yet.

[0004]

Means for Solving the Problems The present inventors have made intensive studies on epoxy resins having the above-mentioned characteristics, and have completed the present invention. That is, according to the present invention, the formula (1)

[0005]

Embedded image

(Wherein, X represents a hydrocarbon group having 1 to 14 carbon atoms or a hydroxy hydrocarbon group. A represents an integer of 1 to 6, b represents an integer of 1 to 5, and R represents each independently. Represents a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 8 carbon atoms or an aryl group, and n represents an average value of 1 to 10.) and a phenolic compound represented by (b) 4,
An epoxy resin obtained by glycidylation of a mixture of 4'-dihydroxybiphenyl having a softening point of 120
(2) (the blending amount of component (b) in a mixture of component (a) and component (b) x 1.6) / (component (a) and component (b) The modified epoxy resin according to the above (1) or (2), wherein the blending amount of the component (a) in the mixture of (1) × (1 + 56 / hydroxyl equivalent of the component (a))) is 0.3 or less; (1) or (2) above, wherein X is a hydrocarbon group having 8 to 14 carbon atoms in (1).
The modified epoxy resin as described in (4), wherein the compound of the formula (1) is 1,1-bis- (4-hydroxyphenyl) -3,3,3.
The above (1) to 5-trimethyl-cyclohexane,
The modified epoxy resin according to any one of (3),
(5) The compound of the formula (1) is a compound of the formula (2)

[0007]

Embedded image

Wherein c is an integer of 1 to 6, and d is 1 to 5
Are respectively shown. P independently represents a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 8 carbon atoms or an aryl group. m shows an average value of 1 to 10. The modified epoxy resin according to any one of the above (1) to (3), wherein the modified epoxy resin according to the above (1), wherein the component (a) is an alkylphenol novolak,
(7) The modified epoxy resin according to the above (6), wherein the component (a) is o-cresol novolac, and (8) the component (a) (weight of binuclear component) / (weight of trinuclear component). The modified epoxy resin according to (6) or (7), wherein the value is 0.4 or less, the proportion of the tetranuclear component of the component (a) is 30% by weight or more, and the total proportion of the 1-3 nuclear components The modified epoxy resin according to any one of the above (6) to (7), wherein the component (a) has a carboxyl group and an alcoholic hydroxyl group in one molecule. The modified epoxy resin according to any one of the above (6) to (9), which is an alkylphenol novolak obtained by condensing an alkylphenol and formaldehyde with the catalyst as a catalyst, wherein the component (a) (11) has a softening point of 100 ° C.
(7) to the following o-cresol novolaks
(10) the modified epoxy resin according to any one of the above,
(12) In the mixture of the component (a) and the component (b), the weight ratio of the component (a) and the component (b) is (b) /
The modified epoxy resin according to any one of the above (1) to (11), wherein (a) is 0.4 or less, (13) component (a) in a mixture of component (a) and component (b). The ratio of the amount of the component (b) blended is (b) / (a) in a weight ratio of 0.1.
The modified epoxy resin according to any one of the above (1) to (11), wherein the modified epoxy resin is less than 25 and 0.05 or more, and (14) the modified epoxy resin according to any one of the above (1) to (13). (15) The epoxy resin composition according to the above (14) prepared for semiconductor encapsulation, (16) the epoxy resin composition according to the above (14) or (15), A cured product comprising:

[0009]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The modified epoxy resin of the present invention comprises a phenolic compound represented by the formula (1) (component (a), hereinafter simply referred to as (a)) and 4,4'-dihydroxybiphenyl (component (a)). b) (hereinafter simply referred to as (b)) (hereinafter simply referred to as a phenol mixture) and epihalohydrins. Thereby, even if the glycidylated compound of the compound of the formula (1) alone is semisolid or liquid, it is glycidylated as a mixture with 4,4′-dihydroxybiphenyl, so that it has a softening point while having the same viscosity or less. A highly modified epoxy resin can be obtained. The mixing ratio of (a) and (b) in the phenol mixture is not particularly limited, but is usually not more than 0.4, preferably less than 0.25, preferably not less than 0.05 as a value of (b) / (a) by weight. It is. Also,
(Blending amount of (b) in mixture of (a) and (b) ×
1.6) / (the amount of (a) in the mixture of (a) and (b) × (1 + 56 / (hydroxy equivalent of (a))) is 0.3
Hereinafter, it is preferably 0.05 or more. If the amounts of (a) and (b) deviate from the above ranges, crystals will precipitate during the synthesis of the modified epoxy resin. Problems such as heat resistance and moisture resistance, and the modified epoxy resin synthesized using the low molecular weight (a) does not have crystallinity and is not solidified, and the viscosity is not sufficiently reduced. A dot may appear.

Specific examples of the compound of the formula (1) that can be used include bisphenol A, bisphenol F, 1,1-bis- (4-hydroxyphenyl) -cyclohexane,
1,1-bis- (4-hydroxyphenyl) -3,3,3
5-trimethylcyclohexane, terpene diphenol, phenol novolak, phenol / dicyclopentadiene polymer, phenol / xylylene glycol polycondensate, compound of formula (2), phenol and compound of formula (2) Examples thereof include, but are not limited to, condensates, polycondensates of phenols / hydroxybenzaldehydes, and alkylphenol novolaks obtained by condensing phenols having an alkyl group with formaldehyde. Phenols in the above polycondensates include phenol, cresol, xylenol, tert-
Butyl-cresol, naphthol and the like,
It is not limited to these. Further, among these compounds, 1,1-bis- (4-hydroxyphenyl)-
3,3,5-trimethyl-cyclohexane, terpene diphenol, phenol / dicyclopentadiene polymer, phenol / xylylene glycol polycondensate, compound of the formula (2), phenol / hydroxybenzaldehyde polycondensate and Alkylphenol novolaks are preferred and 1,1-bis- (4-hydroxyphenyl)
-3,3,5-trimethyl-cyclohexane, formula (2)
Or an alkylphenol novolak is particularly preferred. In addition, o-cresol novolak is preferable among the alkylphenol novolaks, and has a softening point of 100.
Particularly preferred is o-cresol novolak at a temperature of at most 0C.

One of the characteristics of the modified epoxy resin of the present invention is that no blocking occurs. When an alkylphenol novolak is selected as the compound of the formula (1), the aromatic epoxy contained in the molecule of the alkylphenol novolak is used. The effect is more remarkable when the number of low nucleus components (particularly, binuclear) having a small number of rings is small. Therefore,
Alkylphenol novolak having a value of (weight of binuclear component) / (weight of trinuclear component) of 0.4 or less;
The nucleus component is 30% by weight or more and the total of 1 to 3 nucleus components is 20% by weight or less, preferably 35 to 10%.
0% by weight and the total of 1-3 core components is 0-15% by weight
It is more preferable to use an alkylphenol novolak which is In the above and the following alkylphenol novolaks, the x-nucleus refers to a molecule in which the number of aromatic rings contained in the molecule of the alkylphenol novolak is x. The weight ratio of the x nucleus can be measured by GPC (gel permeation chromatography) or the like.

The above-mentioned alkylphenol novolak having a low content of low nuclei is removed by, for example, molecular distillation or washing with water, or a mononuclear dimethylol or a dinuclear dimethylol of alkylphenol is once synthesized. And a method of condensing these with an excess alkylphenol. However, the above method has many steps and is costly. As a method for solving this point, for example, a method of condensing an alkylphenol and formaldehyde using an oxycarboxylic acid having an alcoholic hydroxyl group and a carboxyl group in one molecule as a catalyst as described in JP-A-8-3257. There is. Compared to the case where a normal catalyst is used, an alkylphenol novolak having a small amount of low nucleus components and a narrow molecular weight distribution can be obtained. Examples of the oxycarboxylic acid used in this reaction include lactic acid, malic acid, mandelic acid, tartaric acid, citric acid, and the like.
Two or more kinds may be used in combination. Further, hydrochloric acid, sulfuric acid, oxalic acid, p
-Toluenesulfonic acid and the like may be used in combination. The amount of the oxycarboxylic acid to be used is generally 0.01 to 5.0 mol, preferably 0.05 to 1.0 mol of formaldehyde.
４4.0 mol, more preferably 0.1-3.0 mol. The condensation reaction may be performed at a reflux temperature or lower for 1 to 10 hours. After completion of the reaction, the solvent or unreacted alkylphenol and formaldehyde are removed under heating and reduced pressure after removing the catalyst oxycarboxylic acid by repeating washing with water as it is or dissolving it in a solvent such as toluene, xylene, methyl isobutyl ketone. .

Specific examples of epihalohydrins used in the glycidylation reaction for obtaining the modified epoxy resin of the present invention include epichlorohydrin, β-methylepichlorohydrin, epibromhydrin, β-methylepibromhydrin, epiiodine Hydrin, β-ethyl epichlorohydrin and the like can be mentioned, but epichlorohydrin, which is easily available industrially and is inexpensive, is preferable. This glycidylation reaction itself can be performed according to a conventionally known method.

For example, a solid of alkali metal hydroxide such as sodium hydroxide, potassium hydroxide or the like is added to the above-mentioned mixture of phenol mixture and epihalohydrin in a lump or gradually, usually at 20 to 120 ° C. for 0.5 to 10 minutes.
Let react for 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 distilled off, the resulting distillate is separated, water is removed, and epihalohydrins are continuously returned to the reaction mixture.

In the above method, the amount of the epihalohydrin used is usually 0.5 to 10 mol, preferably 1.0 to 6.0 mol, per equivalent of the hydroxyl group of the phenol mixture. The amount of the alkali metal hydroxide to be used is generally 0.5 to 1.5 mol, preferably 0.7 to 1.2 mol, per 1 equivalent of the hydroxyl group in the phenol mixture. Also, dimethyl sulfone, dimethyl sulfoxide, dimethylformamide,
By adding an aprotic polar solvent such as 1,3-dimethyl-2-imidazolidinone, a modified epoxy resin having a low hydrolyzable halogen concentration defined below is obtained,
This modified epoxy resin is suitable for use in sealing electronic materials. The amount of the aprotic polar solvent used is usually 5 to 200% by weight, preferably 10 to 10% by weight based on the epihalohydrin.
0% by weight. In addition to the above-mentioned solvents, the reaction is facilitated by addition of alcohols such as methanol and ethanol, and cyclic ethers such as 1,4-dioxane. It is higher than the case, but lower than when these solvents are not used. Further, toluene, xylene and the like can be used. Here, the concentration of the hydrolyzable halogen can be measured, for example, by placing the modified epoxy resin in a dioxane and 1N-KOH / ethanol solution, refluxing for several tens minutes, and then titrating with a silver nitrate solution.

A quaternary ammonium salt such as tetramethylammonium chloride, tetramethylammonium bromide or trimethylbenzylammonium chloride is used as a catalyst in a mixture of a phenol mixture and an excess of epihalohydrins, usually at 50 to 150 ° C.
The reaction is performed for 10 hours, and a solid or aqueous solution of an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide is added to the resulting halohydrin ether of the phenol mixture,
The modified epoxy resin of the present invention can also be obtained by reacting at 20 to 120 ° C. for 1 to 10 hours to close the ring of the halohydrin ether. In this case, the amount of the quaternary ammonium salt used is 0.00 to 1 equivalent of the hydroxyl group of the phenol mixture.
It is 1 to 0.2 mol, preferably 0.05 to 0.1 mol. The amount of the alkali metal hydroxide to be used is generally 0.8 to 1.5 mol, preferably 0.9 to 1.1 mol, per 1 equivalent of the hydroxyl group of the phenol mixture.

In general, these reaction products are used after washing with or without washing with water, and excess epihalohydrins,
After removing the solvent and the like, the residue 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. The modified epoxy resin of the present invention having a low concentration can be obtained. In this case, the amount of the alkali metal hydroxide to be used is 0.01 to 0.1 with respect to 1 equivalent of the hydroxyl group of the phenol mixture.
It is 2 mol, preferably 0.05 to 0.1 mol. The reaction temperature is usually 50 to 120 ° C, and the reaction time is usually 0.5 to 2
Time. After the reaction is completed, salts formed as by-products are removed by filtration, washing with water, etc., and the modified epoxy resin of the present invention having a low hydrolyzable halogen concentration is obtained by distilling off solvents such as toluene, methyl isobutyl ketone and methyl ethyl ketone under reduced pressure under heating. Obtainable. The modified epoxy resin of the present invention thus obtained has the following formula (A)

[0018]

Embedded image

(Wherein X, R, a and b have the same meanings as in formula (1)), which contains a trace amount of a compound having a bond represented by the formula: Therefore, (a), (b)
Compared to a mixture of single glycidyl compounds,
The familiarity of each epoxy resin component is improved, and when blended with the epoxy resin composition of the present invention described later, the adhesion to other components is improved, and the storage stability (blocking resistance) of the epoxy resin composition is improved. I do. The modified epoxy resin of the present invention has a softening point of 120 ° C or lower and 60 ° C or higher. If the softening point is less than 60 ° C., the storage stability is poor, and if it exceeds 120 ° C., the workability is reduced when kneading the epoxy resin composition using a kneader or the like, or kneading unevenness of the epoxy resin composition occurs. Or

Hereinafter, the epoxy resin composition of the present invention will be described. In the epoxy resin composition of the present invention, the modified epoxy resin of the present invention can be used alone or in combination with another epoxy resin. When used in combination, the proportion of the modified epoxy resin of the present invention in the total epoxy resin is preferably 30% by weight or more, particularly preferably 40% by weight or more.

Specific examples of other epoxy resins that can be used in combination with the modified epoxy resin of the present invention include bisphenols,
Phenols (phenol, alkyl-substituted phenol,
Naphthol, alkyl-substituted naphthol, dihydroxybenzene, dihydroxynaphthalene, etc.) with various aldehydes, polymers of phenols with various diene compounds, polycondensates of phenols with aromatic dimethylols, biphenols, alcohols Glycidyl ether-based epoxy resins, alicyclic epoxy resins, glycidylamine-based epoxy resins, glycidyl ester-based epoxy resins, etc., obtained by glycidylation of glycidyl groups and the like are not limited thereto. These may be used alone or in combination of two or more.

The epoxy resin composition of the present invention contains a curing agent in a preferred embodiment. As the 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, imidazo -
BF ₃ -amine complex, guanidine derivative and the like. The amount of the curing agent used is preferably 0.5 to 1.5 equivalents to 1 equivalent of the epoxy group of the epoxy resin,
-1.2 equivalents is particularly preferred. 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.

The epoxy resin composition of the present invention may further contain, if necessary, fused silica, crystalline silica, porous silica, alumina, zircon, calcium silicate, calcium carbonate, silicon carbide, silicon nitride, boron nitride, zirconia,
Aluminum nitride, forsterite, steatite,
Powders such as spinel, mullite, titania, talc, etc., or various fillers such as inorganic fillers, silane coupling agents, mold release agents, pigments, etc., made of these spherical or crushed, and various thermosetting resins are added. can do. In particular, when an epoxy resin composition for semiconductor encapsulation is obtained, the amount of the inorganic filler used is usually 8% in the epoxy resin composition.
It is in the range of 0-92% by weight, preferably 83-90% by weight, more preferably 85-90% by weight.

The epoxy resin composition of the present invention is obtained by uniformly mixing the above-mentioned components at the above-mentioned ratios, and is preferably used for semiconductor encapsulation. 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, an epoxy resin and a curing agent, and if necessary, a curing accelerator, an inorganic filler, a compounding agent, and various thermosetting resins are made uniform using an extruder, a kneader, a roll, or the like as necessary. The epoxy resin composition of the present invention is obtained by sufficiently mixing the epoxy resin composition and the epoxy resin composition by a melt casting method or a transfer method.
The cured product of the present invention can be obtained by molding by a molding method, an injection molding method, a compression molding method, or the like, and heating at 80 to 200 ° C. if necessary.

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 base material and drying by heating may be subjected to hot press molding to obtain the cured product of the present invention.

In this case, the solvent accounts for usually 10% of the total weight of the epoxy resin composition of the present invention and the solvent.
７０70% by weight, preferably 15-65% by weight.

[0028]

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 epoxy equivalent, melt viscosity, softening point, and weight ratio of the x nucleus were measured under the following conditions. In Examples and Comparative Examples, parts means parts by weight. Epoxy equivalent Measured in accordance with JIS K-7236, unit is g
/ Eq. Melt viscosity Melt viscosity in cone plate method at 150 ° C Measurement machine: cone plate (ICI) high temperature viscometer (RESE)
ARCH EQUIPMENT (LONDON) LTD. : 3 (measurement range: 0 to 20 poise) Sample amount: 0.15 ± 0.01 g Softening point Measured by a method according to JIS K-7234 Blocking resistance 1.5 liters of a marbled epoxy resin having a diameter of about 5 mm 1 kg was placed in a PET bottle, and after standing in a thermostat at 35 ° C. for 72 hours, the welding condition of the epoxy resin was checked. In addition, the evaluation result was shown in the column of blocking resistance in Table 5 based on the following criteria. ◎: Marbles are not welded to each other 若干: Slightly welded but can be broken apart by hand △: Significantly welded X: Weight ratio of x nuclei completely formed into one resin mass Sample was analyzed with a GPC analyzer and determined from the area percentage of peaks corresponding to each component. GPC analysis conditions Column: Shodex KF-803 (2) + KF-802.5 (2) Column temperature: 40 ° C Solvent: tetrahydrofuran Detection: UV (254 nm) Flow rate: 1 ml / min.

Example 1 1,1-bis- (4-hydroxyphenyl) -3,3
55 parts of 5-trimethylcyclohexane, 15.6 parts of 4,4′-hydroxybiphenyl, 194 parts of epichlorohydrin (ECH, the same applies hereinafter), and 100 parts of dimethyl sulfoxide (DMSO, the same applies hereinafter) are charged into a reaction vessel, heated, stirred, After dissolution, while maintaining the temperature at 45 ° C., the inside of the reaction system was maintained at 45 Torr, and 54 parts of a 40% aqueous sodium hydroxide solution was continuously dropped 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 carried out at 70 ° C for 2 hours and at 70 ° C for 30 minutes. Subsequently, washing with water was repeated to remove by-product salts and dimethyl sulfoxide. After that, excess epichlorohydrin was distilled off from the oil layer under heating and reduced pressure, and 200 parts of methyl isobutyl ketone was added to the residue to dissolve the residue. The solution of methyl isobutyl ketone was heated to 70 ° C., 4 parts of a 30% aqueous sodium hydroxide solution was added, and the mixture was reacted for 1 hour. Then, the reaction solution was repeatedly washed with water until the washing solution became neutral. Then, methyl isobutyl ketone was distilled off from the oil layer under heating and reduced pressure to obtain the modified epoxy resin (E1) 94 of the present invention.
Got a part.

Example 2 The same operation as in Example 1 was performed except that ECH was changed to 150 parts. As a result, 95 parts of the modified epoxy resin (E2) of the present invention was obtained.

Example 3 The same operation as in Example 1 was performed except that ECH was changed to 100 parts. As a result, 93 parts of the modified epoxy resin (E3) of the present invention was obtained.

Example 4 In Example 2, 1,1-bis- (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane was added to 59
The same operation as in Example 2 was performed except that 12.5 parts of 4,4′-hydroxybiphenyl and 53 parts of a 40% aqueous sodium hydroxide solution were used. As a result, 96 parts of the modified epoxy resin (E4) of the present invention was obtained.

Example 5 In Example 2, 1,1-bis- (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane was replaced with a dicyclopentadiene / phenol polymer (DPP series manufactured by Nippon Petrochemical Co., Ltd., softening point 89 ° C.) ) 58,4,4 '
The same operation as in Example 2 was performed, except that 1-hydroxybiphenyl was used in 14.4 parts and the 40% aqueous sodium hydroxide solution was used in 53 parts. As a result, 92 parts of the modified epoxy resin (E5) of the present invention was obtained.

Example 6 In Example 2, 1,1-bis- (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane was converted to a phenol / xylylene glycol polycondensate (Mirex X
L-225-4L, manufactured by Mitsui Toatsu Chemicals, Inc., softening point 52
C) 54 parts of 4,4'-hydroxybiphenyl
The same operation as in Example 2 was performed, except that the aqueous solution of 40% sodium hydroxide was changed to 52 parts to 7.5 parts. As a result, a modified epoxy resin (E6) part of the present invention was obtained.

Example 7 In Example 2, 1,1-bis- (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane was converted to terpene diphenol (YP-Chemical Co., Ltd., YP-
90) 54, 4 parts of 4,4'-hydroxybiphenyl
The same operation as in Example 2 was performed, except that the aqueous solution of 40% sodium hydroxide was changed to 52 parts to 7.5 parts. As a result, 97 parts of the modified epoxy resin (E7) of the present invention was obtained.

Example 8 In Example 2, 1,1-bis- (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane was replaced by the following formula (3)

[0037]

Embedded image

Compound (softening point 155 ° C., m =
1.1 (average value)) The same operation as in Example 2 was performed except that 62 parts, 4,4'-hydroxybiphenyl was changed to 12.5 parts, and a 40% aqueous sodium hydroxide solution was changed to 46 parts. . As a result, the modified epoxy resin (E8) 95 of the present invention was obtained.
Got a part.

Example 9 In Example 2, 1,1-bis- (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane was converted to a phenol / salicylaldehyde polycondensate (softening point 110
° C, ICI viscosity 9.2 poise) in 45.6 parts,
Example 2 except that 4'-hydroxybiphenyl was changed to 17.5 parts and 40% aqueous sodium hydroxide solution was changed to 66 parts.
The same operation as described above was performed. As a result, 94 parts of the modified epoxy resin (E9) of the present invention was obtained.

Example 10 In Example 2, 1,1-bis- (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane was reacted with a phenol / salicylaldehyde polycondensate (softening point 110
° C, ICI viscosity 9.2 poise)
The same operation as in Example 2 was performed except that 18.6 parts of 4'-hydroxybiphenyl and 100 parts of a 40% aqueous sodium hydroxide solution were used. As a result, 141 parts of the modified epoxy resin (E10) of the present invention was obtained.

Example 11 In Example 2, 1,1-bis- (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane was reacted with a phenol / salicylaldehyde polycondensate (softening point 120
C) 83 parts, 4,4'-hydroxybiphenyl 17
The same operation as in Example 2 was carried out except that the amount of the 40% aqueous sodium hydroxide solution was changed to 104 parts. As a result, 145 parts of the modified epoxy resin (E11) of the present invention was obtained.

Comparative Example 1 In Example 1, only 1,1-bis- (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane was used without using 4,4'-dihydroxybiphenyl.
The same operation as in Example 1 was performed except that one copy was used. As a result, 105 parts of an epoxy resin (R1) was obtained.

Comparative Example 2 In Comparative Example 1, 1,1-bis- (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane was replaced with a dicyclopentadiene / phenol polymer (DPP series softening point 89 manufactured by Nippon Petrochemical). The same operation as in Comparative Example 1 was performed except that the temperature was changed to 84 parts. As a result, 107 parts of an epoxy resin (R2) was obtained.

COMPARATIVE EXAMPLE 3 In Comparative Example 1, 1,1-bis- (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane was replaced with MILEX XL-225-4L (softening point 5 manufactured by Mitsui Toatsu Chemicals, Inc.).
(2 ° C.) The same operation as in Comparative Example 1 was performed except that the amount was changed to 85 parts. As a result, 109 parts of an epoxy resin (R3) was obtained.

Comparative Example 4 In Comparative Example 1, 1,1-bis- (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane was replaced with terpene diphenol (YP, manufactured by Yasuhara Chemical Co., Ltd., YP
-90) The same operation as in Comparative Example 1 was performed, except that 84 parts were used. As a result, 110 parts of an epoxy resin (R4) was obtained.

Comparative Example 5 In Comparative Example 1, 1,1-bis- (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane was converted to a phenol / biphenyldimethanol polycondensate (softening point 1
55 ° C) 100 parts, 250 parts of epichlorohydrin, M
The same operation as in Comparative Example 1 was performed, except that the IBK was changed to 250 parts. As a result, the epoxy resin (R5)
118 parts were obtained.

Comparative Example 6 In Comparative Example 1, 1,1-bis- (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane was converted to a phenol-salicylaldehyde polycondensate (softening point 110
(ICI viscosity: 9.2 poise) The same operation as in Comparative Example 1 was performed except that the amount was changed to 51 parts. As a result, 75 parts of an epoxy resin (R6) was obtained.

Tables 1 to 3 show the physical properties of the modified epoxy resin of the present invention and the comparative epoxy resin obtained in the above Examples and Comparative Examples.

[0049]

[Table 1]

[0050]

Table 2 Example 6 7 8 9 10 11 Epoxy equivalent (g / eq) 233 228 256 166 166 165 Softening point (° C) 81 79 97 86 86 87 Melt viscosity (P) 0.5 0.3 0.6 0.5 0.5 0.5

[0051]

Table 3 Comparative Example 1 2 3 4 5 6 Epoxy equivalent (g / eq) 236 242 232 242 262 168 Softening point (° C) 54 55 52 49 61 54 Melt viscosity (P) 0.4 0.6 0.5 0.4 0.8 0.8

Examples 12 and 13, Comparative Examples 7 and 8 The modified epoxy resins (E2) and (E5) of the examples and the epoxy resins (R1) and (R2) of the comparative examples were used. One equivalent of a curing agent (phenol novolak resin (Nippon Kayaku Co., Ltd., PN-8)
0 I, a viscosity of 1.5 poise at 150 ° C., a softening point of 86 ° C., a hydroxyl equivalent of 106 g / eq) and 1 equivalent of a hydroxyl group, and a curing accelerator (triphenylphosphine) in an amount of 1 part per 100 parts of the epoxy resin. A resin molded body was prepared by transfer molding and cured at 160 ° C. for 2 hours and further at 180 ° C. for 8 hours.

Table 4 shows the results obtained by measuring the physical properties of the cured product thus obtained. The measurement of the physical properties was performed under the following conditions. (Examples 17 to 19, Comparative Examples 12 to 14)
・ Temperature of glass transition (TMA): TM-7000 manufactured by Vacuum Riko Co., Ltd. Temperature rise rate 2 ° C./min. -Copper foil peel strength: Measured according to JIS C-6481 (peel strength). Izod impact test: Measured according to JIS K7710.

[0054]

Table 4 Example Comparative Example 12 13 7 8 Epoxy resin E2 E5 R1 R2 Glass transition temperature (° C) 149 136 148 137 Copper foil peel strength (Kg / cm) 2.5 2.7 2.4 2.4. 6 Izod impact test value (Kg / mm ² ) 17 23 16 20

Example 14 o-Cresol novolak (softening point 80 ° C., binuclear 14
Weight%, trinuclear 16% by weight, tetranuclear 15% by weight) 96
Parts, 4,4'-hydroxybiphenyl 18.6 parts, EC
H. 400 parts and dimethyl sulfoxide (DMSO, hereinafter the same) 100 parts were charged into a reaction vessel, heated, stirred, dissolved,
While maintaining the temperature at 45 ° C., the inside of the reaction system was 45 Torr.
And 100 parts of a 40% aqueous sodium hydroxide solution
It was dropped continuously over time. At this time, the ECH and water distilled off by azeotropic distillation are cooled and separated, and the organic layer E
The reaction was performed while returning only CH into the reaction system. After completion of the sodium hydroxide aqueous solution dropping, at 70 ° C for 2 hours at 45 ° C
For 30 minutes. Then, washing with water was repeated to remove by-product salts and dimethyl sulfoxide. Then, excess epichlorohydrin was distilled off from the oil layer under heating and reduced pressure, and 300 parts of methyl isobutyl ketone was added to the residue to dissolve. The solution of methyl isobutyl ketone was heated to 70 ° C., and 5 parts of a 30% by weight aqueous sodium hydroxide solution was added.
After reacting for a period of time, washing of the reaction solution with water was repeated until the washing solution became neutral. Then, methyl isobutyl ketone was distilled off from the oil layer under heating and reduced pressure to obtain 154 parts of the modified epoxy resin (E12) of the present invention. The modified epoxy resin (E12) thus obtained had an epoxy equivalent of 189, a softening point of 89 ° C. and a melt viscosity of 0.4 poise.

Example 15 Example 14 was repeated except that o-cresol novolak was replaced with o-cresol novolac having a softening point of 83 ° C., 5% by weight of binuclear material, 25% by weight of trinuclear material, and 26% by weight of tetranuclear material. Performed the same operation as in Example 1. As a result, 152 parts of the modified epoxy resin (E13) of the present invention was obtained. The resulting modified epoxy resin (E13) had an epoxy equivalent of 192, a softening point of 88 ° C. and a melt viscosity of 0.6 poise.

Example 16 In Example 14, o-cresol novolak was treated with a softening point of 91 ° C., 3% by weight of a binuclear body, 8% by weight of a trinuclear body,
The same operation as in Example 12 was performed, except that 9% by weight of o-cresol novolak was used. As a result, 151 parts of the modified epoxy resin (E14) of the present invention was obtained. The epoxy equivalent of the modified epoxy resin (E14) obtained was 191 g /
eq, softening point 91 ° C. and melt viscosity 1.1 poise.

Comparative Example 9 In Example 14, o-cresol novolak alone was used without using 4,4'-dihydroxybiphenyl.
The same operation as in Example 12 was performed except that the number of parts was changed. As a result, 162 parts of an epoxy resin (R7) was obtained.

Comparative Example 10 In Example 15, o-cresol novolak was used in the same manner as in Example 15 except that 4,4′-dihydroxybiphenyl was not used.
The same operation as in Example 13 was performed, except that the number of parts was changed. As a result, 164 parts of an epoxy resin (R8) was obtained.

Comparative Example 11 In Example 16, o-cresol novolak alone was used without using 4,4'-dihydroxybiphenyl.
The same operation as in Example 14 was performed except that the number of parts was changed. As a result, 162 parts of an epoxy resin (R9) was obtained.

Tests of physical properties and blocking resistance of epoxy resins (E12) to (E14) obtained in Examples 14 to 16 and epoxy resins (R7) to (R9) obtained in Comparative Examples 9 to 11 Table 5 shows the results.

[0062]

Table 5 Example Comparative Example 14 15 16 9 10 11 Epoxy equivalent (g / eq) 189 192 189 196 194 191 Softening point (° C) 89 88 91 55 55 62 Melt viscosity (P) 0.40. 6 1.1 0.9 0.8 1.6 Blocking resistance ○ ◎ ◎ × × △

Examples 17 to 19, Comparative Examples 12 to 14 Modified epoxy resins (E12) to (E1) obtained in the examples.
4) and the epoxy resins (R7) to (R9) of the comparative examples, and a curing agent (phenol novolak resin (Nippon Kayaku Co., Ltd.)
, PN-80, ICI viscosity at 150 ° C 1.5 poise, softening point 86 ° C, hydroxyl equivalent 106g / eq)
A hydroxyl equivalent is blended, and a curing accelerator (triphenylphosphine) is further blended at 1 part per 100 parts of epoxy resin, and a resin molded body is prepared by transfer molding.
For 2 hours and further at 180 ° C. for 8 hours. Table 6 shows the results of measuring the physical properties of the cured product thus obtained.

[0064]

Table 6 Example Comparative Example 17 18 19 12 13 14 Epoxy resin E12 E13 E14 R7 R8 R9 Glass transition temperature (° C) 146 151 157 147 152 152 159 Izod impact test value 13 14 15 11 13 14 (Kg / mm) ² ) Copper foil peel strength (Kg / cm) 2.4 2.3 2.5 2.4 2.2 2.4 2.4

Example 20 In Example 8, the compound of the formula (3) was treated at a softening point of 80 ° C.
The same operation as in Example 2 was carried out except that the amount of 1.3 parts was changed to 64 parts, 4,4'-hydroxybiphenyl was changed to 12 parts, and the 40% aqueous sodium hydroxide solution was changed to 44 parts.
As a result, 95 parts of the modified epoxy resin (E15) of the present invention was obtained. The resulting modified epoxy resin (E15) had an epoxy equivalent of 255, a softening point of 90 ° C, and a melt viscosity of 0.8P.

Examples 21 to 24, Comparative Examples 15 to 18 The modified epoxy resins (E1
2) to (E15) and epoxy resin (R
7) to (R9) and YX-4000 (epoxy equivalent 196 manufactured by Yuka Shell Epoxy Co., Ltd.) (hereinafter referred to as (R1)
0)), a curing agent (phenol novolak resin (Nippon Kayaku Co., Ltd., PN-80, softening point 86 ° C.)), a curing accelerator (triphenylphosphine), a silane coupling agent (KBM403 manufactured by Shin-Etsu Chemical Co., Ltd.) ), Release agent (fine carnauba manufactured by Toa Kasei Co., Ltd.), antimony trioxide, brominated epoxy resin (BRE manufactured by Nippon Kayaku Co., Ltd.)
NS), spherical silica as an inorganic filler (average particle size 30
μm) and crushed silica (average particle size: 5 μm) in the proportions (parts) shown in Table 7, kneaded with a biaxial roll, crushed,
After tableting, the spiral flow was measured under the following conditions. The results are shown in Tables 8 and 9. -Spiral flow Mold: conforming to EMMI-1-66 Mold temperature: 170 ° C Transfer pressure: 70 kg / cm ²

[0067]

Table 7 Example 7 Comparative Example 21 22 23 24 15 16 17 18 Epoxy resin E12 E13 E14 E15 R7 R8 R9 R10 62 62 62 66 63 63 62 63 Curing agent 35 35 35 31 34 34 35 34 Curing accelerator 1 1 1 1.3 1 1 1 1.3 Silane coupling agent 7 7 7 7 7 7 7 7 Release agent 4 4 4 4 4 4 4 4 Antimony trioxide 6 6 6 6 6 6 6 6 Brominated epoxy resin 15 15 15 15 15 15 15 15 spherical silica 610 610 610 610 610 610 610 610 610 crushed silica 260 260 260 260 260 260 260 260 260

The tablet was heated at 175 ° C., 120
A resin molded body was molded by transfer molding under the conditions of seconds, and immediately after that, the following characteristics were measured. The results are shown in Tables 8 and 9. -Hot hardness of molded product: Measured with a Shore hardness tester (D type) immediately after molding. In addition, the same test piece as that for which the following water absorption was measured was used.

After the obtained molded resin was post-cured at 160 ° C. for 2 hours and further at 180 ° C. for 8 hours, the following characteristics were measured. -Glass transition temperature: Measured in the same manner as in Examples 10 to 11. Water absorption: The rate of weight increase (%) before and after boiling a disk-shaped test piece having a diameter of 50 mm and a thickness of 4 mm in water at 100 ° C. for 24 hours.

A 16-pin 42-alloy lead frame on which a silicon chip was mounted was transferred to the tablet at 175 ° C. for 120 seconds at 70 kg / m 2 by transfer molding.
sealed under the conditions of cm ^2, 2 hours at 160 ° C., further 18
The following characteristics were measured using the simulated SOP obtained by post-curing at 0 ° C. for 8 hours, and the results are shown in Tables 8 and 9. Reflow cracking property: After humidification at 85 ° C./85% RH for a predetermined time, immersion in a solder bath at 260 ° C. for 10 seconds, cracks in appearance and peeling of the front and back surfaces of the die pad were observed, and the number of defects was counted.・ Temperature cycle test: -50 ℃ / 30min ~ 150 ℃ /
The number of defects was counted by observing cracks in appearance and peeling of the front and back surfaces of the die pad after performing 200 times for 30/30.

[0071]

Table 8 Example 21 22 23 24 Epoxy resin E12 E13 E14 E15 Spiral flow (inch) 33 32 30 34 Molded product hot hardness 85 85 85 80 Glass transition temperature (° C) 147 151 157 140 Water absorption (%) ) 0.22 0.23 0.22 0.20 Reflow cracking property (number of defects / number of test pieces) Humidification time 24h 0/200 0/200 0/200 0/20 48h 1/20 2/20 2/200 0 / 20 72h 2/20 5/20 4/20 0/20 Temperature cycle test (number of defects / number of test pieces) 1/20 0/20 1/20 0/20

[0072]

Table 9 Comparative Example 15 16 17 18 Epoxy resin R7 R8 R9 R10 Spiral flow (inch) 25 23 23 33 Molded product hot hardness 80 80 85 75 Glass transition temperature (° C) 147 153 158 130 Water absorption (%) ) 0.22 0.22 0.23 0.22 Reflow crackability (number of defectives / number of test pieces) Humidification time 24h 2/20 5/20 4/200 0/20 48h 7/20 11/20 10/20 0 / 20 72h 20/20 20/20 20/20 0/20 Temperature cycle test (number of defects / number of test pieces) 17/20 19/20 19/20 0/20

As is apparent from Tables 1 to 6, a comparative epoxy resin obtained by epoxidizing only the compound of the formula (1)
Although the physical properties of the cured product of the modified epoxy resin of the present invention are almost the same, it is clear that the modified epoxy resin of the present invention has a higher softening point, and is excellent in workability and storage stability of the composition. Particularly, when used in an epoxy resin composition for semiconductor encapsulation, as is clear from Tables 8 and 9, since the viscosity is lower than that of an unmodified epoxy resin, high filling of conventional fillers is impossible. This is possible even with a conventional resin system, and has the advantage of being unmodified, and is superior in moldability and heat resistance to commonly used high-filled epoxy resins.

[0074]

The modified epoxy resin of the present invention has a high softening point, good workability and storage stability (no blocking).
Low melt viscosity. Accordingly, the modified epoxy resin of the present invention can be used as an insulating material for electric and electronic parts (such as a highly reliable semiconductor encapsulating material) and various composite materials such as a laminated board (such as a printed wiring board) and CFRP, an adhesive, and a paint. It is extremely useful when used for

 ──────────────────────────────────────────────────続 き Continued on the front page (31) Priority claim number Japanese Patent Application No. 9-153153 (32) Priority date Hei 9 (May 28, 1997) (33) Priority claim country Japan (JP)

Claims (16)

[Claims] (A) Formula (1) (In the formula, X represents a hydrocarbon group having 1 to 14 carbon atoms or a hydroxy hydrocarbon group. A represents an integer of 1 to 6, b represents 1 to 6.
An integer of 5 is shown. R independently represents a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 8 carbon atoms, or an aryl group. n shows an average value of 1-10. An epoxy resin obtained by glycidylation of a mixture of a phenolic compound represented by the formula (4) and (b) 4,4'-dihydroxybiphenyl, the modified epoxy resin having a softening point of 120 ° C or lower and 60 ° C or higher. 2. The amount of component (b) in the mixture of component (a) and component (b) × 1.6) / (component (a) in the mixture of component (a) and component (b) × (1 + 56 /
The modified epoxy resin according to claim 1, wherein the component (a) has a hydroxyl equivalent of 0.3 or less. 3. The modified epoxy resin according to claim 1, wherein X in the formula (1) is a hydrocarbon group having 8 to 14 carbon atoms. 4. The compound of the formula (1) is 1,1-bis- (4-
The modified epoxy resin according to any one of claims 1 to 3, which is (hydroxyphenyl) -3,3,5-trimethyl-cyclohexane. 5. The compound of the formula (1) is a compound of the formula (2) (In the formula, c represents an integer of 1 to 6, d represents an integer of 1 to 5. P independently represents a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 8 carbon atoms or an aryl group. M represents an average value of 1 to 10.)
3. The modified epoxy resin according to any one of 3. 6. The modified epoxy resin according to claim 1, wherein the component (a) is an alkylphenol novolak. 7. The modified epoxy resin according to claim 6, wherein the component (a) is o-cresol novolak. 8. Component (a) (weight of binuclear component) / (3)
The modified epoxy resin according to claim 6 or 7, wherein the value of (the weight of the core component) is 0.4 or less. 9. The composition according to claim 6, wherein the proportion of the tetranuclear component of the component (a) is 30% by weight or more and the total proportion of the 1 to 3 nucleus components is 20% by weight or less. Modified epoxy resin. 10. The component according to claim 6, wherein component (a) is an alkylphenol novolak obtained by condensing an alkylphenol with formaldehyde using an oxycarboxylic acid having a carboxyl group and an alcoholic hydroxyl group in one molecule as a catalyst. Or the modified epoxy resin according to claim 1. 11. The composition according to claim 1, wherein component (a) has an o-
The modified epoxy resin according to any one of claims 7 to 10, which is cresol novolak. 12. A mixture of the component (a) and the component (b), wherein the ratio of the compounding amount of the component (a) to the component (b) is not more than 0.4 in terms of weight ratio (b) / (a). Item 12. The modified epoxy resin according to any one of items 1 to 11. 13. The weight ratio of component (a) to component (b) in the mixture of component (a) and component (b) is such that (b) / (a) is less than 0.25. The modified epoxy resin according to any one of claims 1 to 11, which is as described above. 14. An epoxy resin composition containing the modified epoxy resin according to any one of claims 1 to 13. 15. The epoxy resin composition according to claim 14, which is prepared for encapsulating a semiconductor. 16. A cured product obtained by curing the epoxy resin composition according to claim 14.