JPH10130364A - Phenols resin, epoxy resin, epoxy resin composition and its hardened material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a phenols resin useful as a raw material or a hardener for an epoxy resin, having a low viscosity and capable of providing a hardened resin capable of manifesting low water-absorbing properties and a high toughness by forming the resin into a specific structure. SOLUTION: This phenols resin has a structure of formula I [R is H, a halogen, a 1-8C alkyl or aryl; (h) is 1-9; (j) is 1 or 2; (m) and (n) are each a number larger than 0 with the proviso that (m+n)<=10]. The objective resin is preferably obtained by performing a condensation polymerization of (A) phenols, (B) a compound of formula II (X is a halogen, methoxy or hydroxyl group) and (C) a compound of formula III so that the molar ratio of the components B/C may be 0.1-4. The component A is preferably used in the proportion of 1.5-15mol per 1mol total of components B and C. An acidic catalyst used for the reaction is, for example, p-toluenesulfonic acid. An epoxy resin is obtained by reacting the objective resin with an epihalohydrin.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an insulating material for electric and electronic parts such as a high-reliability semiconductor encapsulation, and various kinds of materials such as a laminate (printed wiring board) and CFRP (carbon fiber reinforced plastic). The present invention relates to phenolic resins, epoxy resins, epoxy resin compositions, and cured products thereof useful for composite materials, adhesives, paints, 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 electric and electronic fields, with the development thereof, heat resistance, moisture resistance, adhesion, high toughness, low viscosity for high filling of filler, etc. There is a demand for further improvement of the various characteristics.
On the other hand, it is desired to be solid at room temperature in order to improve workability. In addition, as a structural material, a resin that is lightweight and has excellent mechanical properties for aerospace materials, leisure and sports equipment applications, and the like, and also has a low viscosity in order to improve workability is required. 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, the present invention provides:

[0005]

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(Wherein, a plurality of Rs independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 8 carbon atoms or an aryl group. H is an integer of 1 to 9, and j is 1 to 2; M and n each represent an average value;
It is a real number greater than 0 and m + n is 10 or less. In addition,

[0007]

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And base

[0009]

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Are arranged in an arbitrary order. (2) an epoxy resin obtained by glycidylation of the phenolic hydroxyl group of the phenolic resin described in (1), (3) (a) a phenol, and (b) a formula (b) 2)

[0011]

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(Wherein X represents a halogen atom, a methoxy group or a hydroxyl group. A plurality of Rs independently represent a hydrogen atom,
It represents a halogen atom, an alkyl group having 1 to 8 carbon atoms or an aryl group. And a compound represented by formula (3):

[0013]

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(Wherein X represents a halogen atom, a methoxy group or a hydroxyl group. A plurality of Rs independently represent a hydrogen atom,
It represents a halogen atom, an alkyl group having 1 to 8 carbon atoms or an aryl group. In the method for producing a phenolic resin obtained by polycondensing the compound represented by the formula (1), the compounding ratio of the component (b) to the component (c) is (b) / (c) = 0.1 in a molar ratio.
(4) The method for producing a phenolic resin according to the above (1), wherein the phenolic hydroxyl group of the phenolic resin obtained by the production method according to the above (3) is glycidylated. (5) an epoxy resin composition containing the phenolic resin described in the above (1) or (3); (6) an epoxy resin containing the epoxy resin described in the above (2) or (4) (7) an epoxy resin composition containing the phenolic resin described in the above (1) or (3) and the epoxy resin described in the above (2) or (4); (8) prepared for semiconductor encapsulation The epoxy resin composition according to any one of the above (5), (6) and (7), (9) any one of the above (5), (6), (7) and (8) Epoxy tree described in item A cured product obtained by curing the composition.

[0015]

BEST MODE FOR CARRYING OUT THE INVENTION The phenolic resin of the present invention comprises, for example, (a) a phenol, (b) a compound of the formula (2), and (c) a compound of the formula (3), if necessary. By heating and polycondensation in the presence of

Specific examples of phenols that can be used as component (a) include phenol, cresol, ethylphenol, tert-butylphenol, 2,5-dimethylphenol, alkylphenols such as 2-tertbutyl-5-methylphenol, and guaiacol. , Guetor, allylphenol, hydroquinone, resorcinol,
Examples include, but are not limited to, catechol, naphthol, and dihydroxynaphthalene, and these may be used alone or in combination of two or more. The amount of the phenol used is usually 1 to 1 mol of the component (b) + the component (c).
20 mol, preferably 1.5 to 15 mol. Also,
The compounding ratio of the component (b) represented by the formula (2) and the component (c) represented by the formula (3) is (b) / (c), usually 0.05 to 10, preferably 0. .

Examples of the acid catalyst include hydrochloric acid, phosphoric acid, sulfuric acid,
Formic acid, zinc chloride, ferric chloride, p-toluenesulfonic acid and the like can be mentioned. These may be used alone or in combination of two or more. The amount of the catalyst to be used is generally 0.01 to 10% by weight, preferably 0.05 to 5% by weight, based on the total weight of component (a) + component (b) + component (c).

The reaction temperature is 100 to 250 ° C. and the reaction time is 1 to 20 hours. Alcohol, water and hydrogen halide which grow during the reaction are appropriately trapped outside the system. Also,
Unreacted phenols are removed by deactivating or removing the acidic catalyst after completion of the reaction, and then distilling off under heating vacuum or distilling off by steam distillation or the like.

The epoxy resin of the present invention can be obtained by reacting the phenolic resin obtained by the above method with epihalohydrin as a raw material. Specific examples of the epihalohydrins that can be used in the epoxidation reaction include epichlorohydrin, β-methyl epichlorohydrin, epibromohydrin, β-methyl epibromohydrin, epiiodohydrin, β-ethyl epichlorohydrin, and the like. However, epichlorohydrin, which is industrially available and inexpensive, is preferred. This epoxidation reaction can be performed according to a conventionally known method.

The epoxidation reaction is carried out, for example, by adding a solid of alkali metal hydroxide such as sodium hydroxide or potassium hydroxide to a mixture of the above-mentioned phenolic resin and epihalohydrin at a temperature of 20 to 120 ° C.
For 0.5 to 10 hours. At this time, an aqueous solution of the alkali metal hydroxide may be used. In such a case, the alkali metal hydroxide is continuously added, and water and epihalohydrin are continuously added to the reaction mixture under reduced pressure or normal pressure. May be further distilled off, water may be removed therefrom, and epihalohydrins may be 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 5.0 mol, per equivalent of the hydroxyl group of the phenol resin. 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. Dimethyl sulfone,
Dimethylsulfoxide, dimethylformamide, 1,3
By adding an aprotic polar solvent such as -dimethyl-2-imidazolidinone, an epoxy resin having a low concentration of hydrolyzable halogen as defined below is obtained, and this epoxy resin is suitable for use in sealing electronic materials. . The amount of the aprotic polar solvent used is 5 to the weight of the epihalohydrin.
The content is from 200 to 200% by weight, preferably from 10 to 100% by weight. In addition to the above solvents, methanol, alcohols such as ethanol, and the addition of cyclic and chain ethers such as 1,4-dioxane facilitate the reaction,
The concentration of the hydrolyzable halogen is also higher than when the aprotic polar solvent is used, but lower than when these solvents are not used. Further, toluene, xylene and the like can be used. Here, the hydrolyzable halogen concentration can be measured, for example, by placing the 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 phenolic resin and an excess epihalohydrin at 50 ° C. to 150 ° C. 1
After reacting for 0 hour, 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 phenolic resin,
The epoxy resin of the present invention can also be obtained by reacting at 0 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 usually 0.001 to 1 equivalent of the hydroxyl group of the phenolic resin.
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 equivalent of the hydroxyl group of the phenolic resin.

Usually, these reaction products are washed with water or without water, and then heated under reduced pressure to obtain an excess of epihalohydrins,
After removing the used solvent and the like, the mixture is dissolved in a solvent such as toluene, methyl isobutyl ketone, and methyl ethyl ketone, and an aqueous solution of an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide is added thereto, and the reaction is carried out again. An epoxy resin having a low decomposable halogen concentration can be obtained. In this case, the amount of the alkali metal hydroxide used is usually 0.01 to 1 equivalent of the hydroxyl group of the phenolic resin.
To 0.2 mol, preferably 0.05 to 0.1 mol. The reaction temperature is usually between 50 and 120 ° C., and the reaction time is usually 0.5 to 2 hours. After the completion of the reaction, salts produced as by-products are removed by filtration, washing with water, and the like, and the epoxy resin of the present invention having a low hydrolyzable halogen concentration can be obtained by distilling off solvents such as toluene and methyl isobutyl ketone under reduced pressure with heating. it can.

Hereinafter, the epoxy resin composition of the present invention will be described. In the epoxy resin composition according to (5) or (8), the phenolic resin of the present invention acts as a curing agent for the epoxy resin. In this case, the phenolic resin of the present invention is used alone or in combination with another curing agent. I can do it. When used in combination, the proportion of the phenolic resin of the present invention in the total curing agent is preferably at least 20% by weight, particularly preferably 3% by weight.
0% by weight or more is preferred.

Other curing agents that can be used in combination with the phenolic resin of the present invention include, for example, amine compounds, acid anhydride compounds, amide compounds, phenol compounds and the like. 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, trimellitic anhydride, pyromellitic anhydride, maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylnadic anhydride,
Hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, bisphenols, phenol (phenol,
Polycondensates of alkyl-substituted phenols, naphthol, alkyl-substituted naphthol, dihydroxybenzene, dihydroxynaphthalene, etc.) with various aldehydes, polymers of phenols with various diene compounds, polycondensates of phenols with aromatic dimethylol, Biphenols and modified products thereof, imidazole, BF ₃ -amine complex, guanidine derivative and the like can be mentioned.

In the epoxy resin compositions described in the above (6) and (8), the epoxy resin of the present invention can be used alone or in combination with other epoxy resins. When used in combination, the proportion of the epoxy resin of the present invention in the total epoxy resin is preferably 30% by weight or more, particularly 40% by weight.
The above is preferred.

Specific examples of other epoxy resins that can be used in combination with the epoxy resin of the present invention include bisphenols, phenols (phenol, alkyl-substituted phenol, naphthol, alkyl-substituted naphthol, dihydroxybenzene, dihydroxynaphthalene, etc.) and various aldehydes. Polycondensates of phenols and various diene compounds, polycondensates of phenols and aromatic dimethylol,
Glycidyl ether-based epoxy resins obtained by glycidylation of biphenols, alcohols, etc., alicyclic epoxy resins, glycidylamine-based epoxy resins, glycidyl ester-based epoxy resins, and the like are included. It is not something to be done. These may be used alone or in combination of two or more.

In the epoxy resin compositions (7) and (8), when the phenolic resin of the present invention is used as a curing agent, the epoxy resin exemplified above as the other epoxy resin or the epoxy resin of the present invention may be used. Epoxy resin can be used.

In the epoxy resin compositions (7) and (8), when the epoxy resin of the present invention is used as the epoxy resin, the curing agent exemplified above as the other curing agent or the curing agent of the present invention may be used. Phenolic resins can be used.

The amount of the curing agent used in the epoxy resin composition of the present invention is usually 0.5 to 1.5 equivalents, preferably 0.6 to 1.
Two 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.

The epoxy resin composition of the present invention may contain a curing accelerator if necessary. Specific examples of the curing accelerator that can be used include imidazoles such as 2-methylimidazole, 2-ethylimidazole and 2-ethyl-4-methylimidazole, and tertiary amines such as 2- (dimethylaminomethyl) phenol. And phosphines such as triphenylphosphine, and metal compounds such as tin octylate. The hardening accelerator is used in an amount of 0.01 to 15 parts by weight based on 100 parts by weight of the epoxy resin as required. Further, the epoxy resin composition of the present invention may contain various additives such as fillers such as silica, alumina and talc, silane coupling agents, release agents and pigments, if necessary.

The epoxy resin composition of the present invention can be obtained by uniformly mixing the above components at a predetermined ratio.
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 a curing agent, if necessary, a curing accelerator, a filler and other compounding agents are sufficiently mixed, if necessary, using an extruder, a kneader, a roll, or the like until they become uniform. To obtain an epoxy resin composition of the present invention, and molding the epoxy resin composition by a melt casting method, a transfer molding method, an injection molding method, a compression molding method, and the like. To obtain the cured product of the present invention.

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

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

[0035]

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, ICI viscosity and softening point were measured under the following conditions. Epoxy equivalent It measured by the method according to JISK-7236. . ICI 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 Softening point Measured by a method according to JIS K-7234

Example 1 A flask equipped with a condenser and a stirrer was charged with 940 parts by weight of phenol and the following formula (4)

[0037]

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169 parts by weight of a compound represented by the following formula (5)

[0039]

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49 parts by weight of the compound represented by the formula (1) and 12 parts by weight of p-toluenesulfonic acid were charged and reacted at 130 to 160 ° C. for 5 hours. At this time, generated methanol was removed from the system as needed. After completion of the reaction, the reaction mixture was neutralized with sodium carbonate, unreacted phenol was distilled off under heating and reduced pressure, dissolved in 400 parts by weight of methyl isobutyl ketone, and washed repeatedly with water to remove salts. Then, unreacted phenol and methyl isobutyl ketone were distilled off under reduced pressure under heating to obtain 380 parts by weight of the phenolic resin (P1) of the present invention. The softening point of the obtained phenolic resin (P1) is 6
1 ° C., ICI viscosity 0.8 poise, hydroxyl equivalent 194
g / eq.

Example 2 A phenolic resin (P) of the present invention was prepared in the same manner as in Example 1 except that phenol was changed to 188 parts by weight.
2) 244 parts by weight were obtained. The obtained phenolic resin (2) has a softening point of 78 ° C., an ICI viscosity of 3.3 poise,
The hydroxyl equivalent was 207 g / eq.

Example 3 In Example 1, the compound of the formula (4) was added to 121 parts by weight,
The same operation was carried out except that the compound of the formula (5) was changed to 82 parts by weight to obtain 252 parts by weight of the phenolic resin (P3) of the present invention. The obtained phenolic resin (P3) has a softening point of 58 ° C., an ICI viscosity of 0.7 poise and a hydroxyl equivalent of 1
It was 86 g / eq.

Example 4 In Example 2, the compound of the formula (4) was added to 121 parts by weight,
The same operation was performed except that the compound of the formula (5) was changed to 82 parts by weight to obtain a phenolic resin (P4) 231 of the present invention. The softening point of the obtained phenolic resin (P4) is 76
° C, ICI viscosity is 3.4 poise, hydroxyl equivalent is 198g
/ Eq.

Example 5 A phenolic resin of the present invention (P5) was prepared in the same manner as in Example 1 except that the compound of the formula (4) was changed to 73 parts by weight and the compound of the formula (5) was changed to 115 parts by weight. ) 238 parts by weight were obtained. The obtained phenolic resin (P5) has a softening point of 54 ° C., an ICI viscosity of 0.5 poise and a hydroxyl equivalent of 1
77 g / eq.

Example 6 A phenolic resin (P5) of the present invention was prepared in the same manner as in Example 2 except that the compound of the formula (4) was changed to 73 parts by weight and the compound of the formula (5) was changed to 115 parts by weight. ) 217 parts by weight were obtained. The obtained phenolic resin (P6) has a softening point of 75 ° C., an ICI viscosity of 3.5 poise and a hydroxyl equivalent of 1
It was 89 g / eq.

Example 7 A reaction vessel was charged with 200 parts by weight of a phenolic resin (P1), 800 parts by weight of epichlorohydrin (ECH, the same applies hereinafter), and 100 parts by weight of dimethyl sulfoxide (DMSO, the same applies hereinafter). While maintaining the temperature at 45 ° C. and maintaining the inside of the reaction system at 45 Torr, 103 parts by weight 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 dropwise addition of the aqueous sodium hydroxide solution, the reaction was further performed at 45 ° C. for 2 hours and at 70 ° C. for 1 hour. Subsequently, washing with water was repeated to remove by-product salts and dimethyl sulfoxide, and then excess epichlorohydrin was distilled off from the oil layer under heating and reduced pressure, and 600 mg
A part by weight of methyl isobutyl ketone was added and dissolved. This solution of methyl isobutyl ketone was heated to 70 ° C.
After adding 10 parts by weight of a 10% aqueous sodium hydroxide solution and reacting for 1 hour, 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 242 parts by weight of the epoxy resin (E1) of the present invention. The epoxy equivalent of the obtained epoxy resin (E1) was 288 g / eq, the softening point was 53 ° C., and the ICI viscosity was 0.7 poise.

Example 8 The procedure of Example 7 was repeated except that the phenolic resin (P1) was changed to 200 parts by weight of the phenolic resin (P2) and the 40% aqueous sodium hydroxide solution was changed to 97 parts by weight. The operation was performed. As a result, 235 parts by weight of the epoxy resin (E2) of the present invention was obtained. The obtained epoxy resin (E2) has an epoxy equivalent of 316 g / eq and a softening point of 68.
C. and an ICI viscosity of 3.0 poise.

Example 9 The same procedure as in Example 1 was carried out except that the phenolic resin (P1) was changed to 200 parts by weight of the phenolic resin (P3) and the 40% aqueous sodium hydroxide solution was changed to 108 parts by weight. The operation was performed. As a result, 221 parts by weight of the epoxy resin (E3) of the present invention was obtained. The obtained epoxy resin (E3) has an epoxy equivalent of 281 g / eq and a softening point of 51.
C. and an ICI viscosity of 0.6 poise.

Example 10 The same as Example 1 except that the phenolic resin (P1) was changed to 200 parts by weight of the phenolic resin (P4) and the 40% aqueous sodium hydroxide solution was changed to 101 parts by weight. The operation was performed. As a result, 230 parts by weight of the epoxy resin (E4) of the present invention was obtained. The obtained epoxy resin (E4) has an epoxy equivalent of 310 g / eq and a softening point of 67.
C., ICI viscosity was 2.9 poise.

Example 11 The same procedure as in Example 1 was carried out except that the phenolic resin (P1) was changed to 200 parts by weight of the phenolic resin (P5) and the 40% aqueous sodium hydroxide solution was changed to 113 parts by weight. The operation was performed. As a result, 235 parts by weight of the epoxy resin (E5) of the present invention was obtained. The obtained epoxy resin (E5) has an epoxy equivalent of 273 g / eq and a softening point of 50.
° C, ICI viscosity 0.5 poise.

Example 12 The same procedure as in Example 1 was carried out except that the phenolic resin (P1) was changed to 200 parts by weight of the phenolic resin (P6) and the 40% aqueous sodium hydroxide solution was changed to 106 parts by weight. The operation was performed. As a result, 233 parts by weight of the epoxy resin (E6) of the present invention was obtained. The obtained epoxy resin (E6) has an epoxy equivalent of 301 g / eq and a softening point of 68.
C., ICI viscosity was 2.8 poise.

Examples 13 to 21 Epoxy resins (E1) to (E6) or o-cresol novolak epoxy resin obtained in Examples (EOCN-1020 manufactured by Nippon Kayaku Co., Ltd.).
Phenol novolak resin (manufactured by Nippon Kayaku Co., Ltd., PN-
(ICI viscosity at 80 and 150 ° C. 1.5 poise, softening point 86 ° C., hydroxyl equivalent 106 g / eq, hereinafter PN) or phenolic resin of the present invention is mixed with one hydroxyl equivalent, and a curing accelerator (triphenylphosphine) is further added. Was blended in an amount of 1 part by weight per 100 parts by weight of the epoxy resin, and a resin molded article was prepared by transfer molding and cured at 160 ° C. for 2 hours and further at 180 ° C. for 8 hours.

The results of measuring the physical properties of the cured product thus obtained are shown in Tables 1 and 2. The physical properties of the cured product are as follows:
It was measured by the following method. -Glass transition temperature (TMA): TM manufactured by Vacuum Riko Co., Ltd.
-7000 Temperature rise rate 2 ° C / min. -Izod impact test: Conducted in accordance with JIS K7710. Water absorption: Weight increase rate (%) after boiling a disc-shaped test piece of 5 cm in diameter x 4 mm in water at 100 ° C for 24 hours.

[0054]

Table 1 Example 13 14 15 16 17 Epoxy resin ECN ECN E1 E2 E3 Curing agent P1 P2 PN PN PN Glass transition temperature (° C.) 137 135 135 133 142 134 Water absorption (%) 0.9 0.90 0.7 0.8 0.7 Izod 17 19 23 20 22

[0055]

Table 2 Example 18 19 20 21 Epoxy resin E4 E5 E6 E1 Curing agent PN PN PN PN Glass transition temperature (° C) 144 130 140 129 Water absorption (%) 0.8 0.8 0.6 0. 3 Izod 19 21 22 29

[0056]

The phenolic resin and the epoxy resin of the present invention both have a lower viscosity than the conventionally known polycondensates of compound (b) and phenols and their epoxidized compounds, and have the compound ( c) A cured product thereof can exhibit lower water absorption and higher toughness than a polycondensation product of c) and phenols and an epoxidized product thereof. It is useful when various composite materials including CFRP (carbon fiber reinforced plastic) and the like, adhesives, paints and the like are used. In particular, when used as a semiconductor encapsulating material, an extremely excellent package crack resistant material can be obtained.

Claims (9)

[Claims] (1) Formula (1) (Wherein, a plurality of Rs independently represent a hydrogen atom, a halogen atom, an alkyl group or an aryl group having 1 to 8 carbon atoms. H is an integer of 1 to 9, and j is an integer of 1 to 2. M and n each represent an average value, are real numbers larger than 0, and m + n is 10 or less. And the group And are arranged in any order. The phenolic resin represented by). 2. An epoxy resin obtained by glycidylating a phenolic hydroxyl group of the phenolic resin according to claim 1. (3) (a) a phenol, (b) a compound of the formula (2) (Wherein X represents a halogen atom, a methoxy group or a hydroxyl group; a plurality of Rs independently represent a hydrogen atom, a halogen atom, a C1-8 alkyl group or an aryl group) and ( c) Formula (3) (Wherein X represents a halogen atom, a methoxy group or a hydroxyl group; a plurality of Rs independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 8 carbon atoms or an aryl group). In the method for producing a phenolic resin obtained by polycondensation, the mixing ratio of the component (b) and the component (c) is (b) / (c) = 0.1 or more in a molar ratio.
The method for producing a phenolic resin according to claim 1, wherein: 4. An epoxy resin obtained by glycidylating a phenolic hydroxyl group of a phenolic resin obtained by the production method according to claim 3. 5. An epoxy resin composition containing the phenolic resin according to claim 1. 6. An epoxy resin composition containing the epoxy resin according to claim 2 or 4. 7. An epoxy resin composition comprising the phenolic resin according to claim 1 or 3 and the epoxy resin according to claim 2 or 4. 8. The epoxy resin composition according to claim 5, which is prepared for encapsulating a semiconductor. 9. A cured product obtained by curing the epoxy resin composition according to any one of claims 5, 6, 7, and 8.