KR960013126B1 - Epoxy resin composition containing phenol aralkyl resin - Google Patents

Abstract

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Description

Epoxy Resin Composition Containing Phenol Aralkyl Resin

Conventionally, many curing agents have been applied to epoxy resin compositions for this purpose. For example, as a curing agent, diethylenetriamine, isophoronediamine, m-xylylenediamine, m-phenylenediamine, 4,4'- Diaminophenylsulfone and other aliphatic or aromatic amine compounds; Phthalic anhydride, trimellitic anhydride, pyromellitic dianhydride, maleic anhydride and other acid anhydrides; Phenol novolak and other phenol resins; Polyamides and modified polyamines; And imidazoles.

However, epoxy obtained by reacting these curing agents with various epoxy resins derived from 2,2 '-(4-hydroxyphenyl) propane, phenol novolak resin, 0-cresol novolak resin and 4,4'-methylenedianiline Resin had both advantages and disadvantages in its properties, making it difficult to satisfy the required properties for the matrix resin.

In recent years, ICs have been increasing in density and density, and therefore, matrix resins for sealing ICs have been required to further improve the level of moisture resistance. However, since the moisture resistance of the matrix resin generally changes inversely to the heat resistance of the resin, when the heat resistant functional group is introduced into the polymer molecule or the density of the functional group is increased to increase the heat resistance, the moisture resistance is lowered. Therefore, IC sealing matrix resins that can satisfy moisture resistance and heat resistance have not been found in the past, and only one of moisture resistance and heat resistance has to be selected according to the use conditions of the matrix resin.

Impact resistance can be improved by imparting flexibility to the cured composition. In recent years, flexibility can be absorbed at break by sea-island structure by adding polyethylene glycol or polypropylene glycol or forming dispersed rubber particles in the resin matrix. By increasing it. However, these methods also significantly reduce heat resistance, causing problems with workability and regeneration.

Moreover, the matrix resin for the heat resistant composition and the heat resistant adhesive needs to be stable for a long time at a use temperature other than heat resistance, moisture resistance and impact resistance, and also requires little deterioration due to light or oxygen in the air.

In order to solve these problems of the matrix resin, there has been a method of replacing the formaldehyde bond of novolak, which is a conventional phenol resin, with a xylene bond (Japanese Patent Application No. 47-15111 (1972)).

The phenol aralkyl resin described in the above publication can be obtained by reacting 1 mole of aralkyl halide or aralkyl alcohol derivative with 1.3 to 3.0 moles, preferably 1.5 to 2.5 moles of phenolic compound, A resin is prepared for the reaction, and the obtained resin can provide a cured product by using hexamethylenetetramine or another known curing agent generally used for novolac. In addition, phenol aralkyl resins that can be used as curing agents for epoxy resins are disclosed in Japanese Patent Application No. 48-10960 (1973), and in any case, fillers such as silica and metal oxides and other additives such as pigments can be mixed. Can be.

As examples of the resin thus obtained, phenol aralkyl resin (trade name, XYLOK, Mitsui Toatsu Chemicale Inc.) derived from phenol is used as an epoxy resin and an IC sealing material (Japanese Patent Office 62-28165 (1987)) and Japanese Patent Application. Location 59-105018 (1984)).

However, matrix resins used in recent synthetic materials require higher levels of heat resistance, mechanical strength, oxidation resistance, and moisture resistance, and phenol aralkyl resins derived from phenol do not satisfy these requirements. In the habit, larger improvement is desired.

Matrix resins used in synthetic materials, i.e., resins containing raw material resins, curing agents and other additives, the raw material resins must have a low melting point, preferably a melting point of 100 DEG C or less, and a resin which is liquid at room temperature. Most preferred.

Resin having a melting point in the above range can improve the workability, for example, it is possible to suppress or avoid overheating during melt kneading or use of solvent when mixing the raw material resin and various additives. When a resin having a softening point of more than 100 ° C. is used as the sealing material, the conductor connecting the substrate to the semiconductor IC is easily deformed or broken due to the high viscosity of the molten resin during the sealing process.

Disclosure of the Invention

An object of the present invention is to improve the moisture resistance of the matrix resin for synthetic materials without compromising heat resistance, oxidation resistance and mechanical strength, and as a curing agent component of epoxy resin, using a resin having excellent low softening point and workability, heat resistance and impact resistance To provide a resin composition excellent in cracking resistance, moisture resistance and workability.

MEANS TO SOLVE THE PROBLEM In order to achieve the said objective, the present inventors used phenolic compounds, such as naphthol or phenylphenol, which are higher molecular weight than phenol as a raw material as a countermeasure for improving the property and workability, ie to increase phenolic properties and improve moisture resistance. In an attempt to reduce the hydroxyl group density in the polymer, for example, a resin produced by a known process disclosed in Japanese Patent Application No. 47-15111 (1972) has a softening point of more than 100 ° C. to improve processability. It was found that this could not be achieved, and the result of intensive research completed the present invention.

That is, one aspect of the present invention is an epoxy resin composition having excellent heat resistance, impact resistance, cracking resistance, moisture resistance and workability, containing 10 to 100% by weight of a low molecular weight phenolaralkyl resin as a curing agent in the total curing agent components. It is about.

Here, resin used for the epoxy resin composition of this invention is Formula (I).

(Wherein X is a divalent group of or n is 0 to 10) and a low molecular weight phenolaralkyl resin having a softening point of 100 ° C. or less, in particular, formula (II)

Low molecular weight phenylphenol aralkyl resins having a softening point of 100 ° C. or less, wherein n is an integer of 0 to 10; And formula (III)

It is a low molecular weight naphthol aralkyl resin whose softening point is 100 degrees C or less represented by (wherein n is an integer of 0-10). In addition, the low molecular-weight phenol aralkyl resin represented by said Formula (I) is Formula (IV)

Wherein R is a mole of aralkyl halide or aralkyl alcohol represented by a halogen atom, a hydroxyl group or a lower alkoxy group having 1 to 4 carbon atoms, and reacts with 3 moles or more of naphthol or phenylphenol in the presence of an acid catalyst. .

The low molecular weight phenol aralkyl resin used in the present invention has a lower hydroxyl group density per unit weight, has the same xylene bond, and is composed of a rigid skeleton of naphthol or phenylphenol as compared to a commercially available XYLOK resin prepared from phenol. .

Accordingly, the cured epoxy resin composition obtained by using an aralkyl resin as the curing agent has almost the same heat resistance and mechanical properties as compared to the cured epoxy resin composition obtained by using a commercially available XYLOK resin as the curing agent, and has excellent moisture resistance.

The hexaamine cured composition of the low molecular weight phenol aralkyl resin used in the present invention tends to have a higher heat deformation temperature because the crosslinking density is increased compared to the hexaamine cured composition of the commercial XYLOK resin.

In addition, phenol aralkyl resins having different softening points can be obtained by changing the molar ratio of naphthol or phenylphenol and aralkyl halide or aralkyl alcohol derivative. That is, it is possible to manufacture a resin in which the range of softening points is appropriately adjusted according to the use conditions.

This softening point is extended to the field of use as the matrix resin of the synthetic material. For example, the epoxy resin composition obtained by using the phenol aralkyl resin of the present invention can be applied to the IC sealing material and the phenol of the present invention. Cured resins crosslinked using aralkyl resins can be applied to brake materials. That is, the possibility of selecting a suitable softening point is a useful property of phenolaralkyl resins.

Best mode for carrying out the invention

The epoxy resin composition of the present invention is obtained by bonding a low molecular weight phenol aralkyl resin to an epoxy resin as a curing agent.

The low molecular weight phenol aralkyl resin used in the present invention is formula (I)

(Wherein X is a bivalent of or n is an integer of 0 to 10). That is, X is a divalent group derived from naphthol or phenylphenol.

In particular, the phenol aralkyl resin is formula (II)

(Wherein n is an integer of 0 to 10) and has a molecular weight of 450 to 3200, a softening point of 100 ° C. or less (by JIS K-2548), or a low molecular weight phenylphenol which is liquid at room temperature. Alkyl resins; And formula (III)

Wherein n is an integer of 0 to 10, and has a molecular weight of 400 to 2850 and a low molecular weight naphthol aralkyl resin having a softening point of 100 ° C. or less or a liquid at room temperature. Preferably, the low molecular weight phenol aralkyl resin contains 40% or more of the compound having n = 0 in the formula (I).

The method for producing the low molecular weight phenol aralkyl resin will be described in detail below.

The low molecular weight phenol aralkyl resin is prepared by reacting one mole of aralkyl halide or aralkyl alcohol derivative represented by the above formula (IV) with 3 moles or more of phenolic compounds in the presence of an acid catalyst.

As a phenolic compound used for the said method, For example, naphthols, such as (alpha)-naphthol and (beta) -naphthol; Phenylphenols such as 0-phenylphenol, m-phenylphenol and P-phenylphenol.

The aralkyl halide or aralkyl alcohol derivative is a compound in which R is a halogen atom such as chlorine or bromine, a hydroxy group or an alkoxy group in formula (IV), and a preferred alkoxy group is a lower alkoxy group having 4 or less carbon atoms, and an alkoxy group having 5 or more carbon atoms is reacted. Slow speed is not desirable. In the butoxy group having 4 carbon atoms, the t-butoxy group is somewhat slow in reaction rate.

Examples of aralkyl halides that may be used include α, α'-dichloro-P-xylene, α, α'-dibromo-P-xylene and α, α '-diiodo-P-xylene, Alkyl alcohol derivatives include α, α'-dihydroxy-P-xylene, α, α '-dimethoxy-P-xylene, α, α'-diethoxy-P-xylene, α, α'-di- n-propoxy-P-xylene, α, α'-diisopropoxy-P-xylene, α, α'-di-n-butoxy-P-xylene, α, α'-di-SeC-part Oxy-P-xylene and α, α'-diisobutoxy-P-xylene.

When the aralkyl halide or aralkyl alcohol derivative represented by formula (IV) is reacted with naphthol or phenylphenol, 3.0 to 20 moles, preferably 3.0 to 10 moles of phenylphenol or naphthol are dissolved in the presence of an acid catalyst. Heated with aralkyl halide or aralkyl alcohol.

If the amount of phenylphenol or naphthol used is large, the content of n = 0 compound in the obtained resin tends to be increased. If it is 3.0 mol or less, the content of n = 0 compound in the obtained resin is 40% or less, and Softening point is undesirable beyond 100 ℃.

The reaction temperature is preferably 110 ° C. or higher. When the temperature is 110 ° C. or lower, the reaction rate is slow, and in order to complete the reaction as soon as possible, 130 to 250 ° C. is preferable and 130 to 180 ° C. is more preferable. The reaction time depends on the reaction temperature but is generally 1 to 30 hours.

Acid catalysts that can be used are inorganic acids and organic acids, for example, inorganic acids such as hydrochloric acid, sulfuric acid and phosphoric acid; Friedel-Crafts catalysts such as zinc chloride, aluminum chloride, ditin tin chloride and ferric chloride; Eutechonic acids, such as methanesulfonic acid and p-toluenesulfonic acid; Sulfate esters such as dimethyl sulfate and diethyl sulfate; And super acids such as trifluoromethanesulfonic acid and boron trifluoride. These catalysts may be used alone or in combination.

The amount of the catalyst used is 0.0001 to 10% by weight, preferably 0.001 to 1% by weight based on the total amount of naphthol or phenylphenol and aralkyl halide or aralkyl alcohol derivative.

Hydrogen halide, water or alcohol generated by the progress of the reaction is distilled off in the reaction system, and after completion of the reaction, unreacted naphthol or phenylphenol is removed from the reaction mixture by vacuum distillation or other suitable method.

Resin which consists of a mixture of the phenol aralkyl compound which has a structure whose n is an integer of 0-10 in said Formula (I) can be obtained by the said process.

The low molecular weight phenol aralkyl resin obtained by the above method can be applied to any kind of epoxy resin as a curing agent.

In addition, the epoxy resin is not limited as long as it has two or more epoxy groups in the molecule.

Useful epoxy resins are obtained by reacting epihalohydrin with a multifunctional compound. Examples of the polyfunctional compound include resorcinol, hydroquinone, bishydroxydiphenyl ether, bishydroxybiphenyl, trihydroxyphenylmethane, tetrahydroxyphenylmethane, tetrahydroxyphenylethane and alkane tetrakisphenol Polyhydric phenols such as dihydroxynaphthalene and condensates thereof; Phenoldicyclopentadiene resin, 0-cresol-dicyclopentadiene resin, p-cresol-dicyclopentadiene resin, m-cresol-dicyclopentadiene resin, m-phenylphenol dicyclopentadiene resin and p-phenyl Phenol dicyclopentadiene condensates, such as phenol dicyclopentadiene resin; Polyhydric alcohols such as resol resin, ethylene glycol, neopentyl glycol, glycerol, trimethylolpropane, pentaerythritol, diethylene glycol and propylene glycol; Amines such as ethylenediamine, aniline and bis (4-aminophenyl) methane; Polycarboxylic acids such as adipic acid, phthalic acid and isophthalic acid.

Epoxy resins that can exhibit particularly excellent effects in the present invention are epihalohydrin, 2,2-bis (4-hydroxyphenyl) propane, 2,2-bis (3,5-dibroco-4- Hydroxyphenyl) propane, bis (4-hydroxyphenyl) methane, phenol-novolak resin, 0-cresol-novolak resin, 4,4'-methylenediamine, formula (V)

(Wherein n is an integer of 0 to 100) a phenol-aralkyl resin represented by formula (VI)

It is obtained by making the resorcinol-aralkyl resin represented by (wherein n is an integer of 0-100).

In the resin composition of the present invention, the phenol aralkyl resin can be used as a curing agent in combination with other known curing agents.

In order to obtain an epoxy resin composition exhibiting high levels of heat resistance, impact resistance, cracking resistance and moisture resistance, the phenol aralkyl resin of the present invention is contained in an amount of 10% by weight or more, preferably 30 to 100% by weight, based on the total amount of the curing agent. Although there is no particular limitation on the ratio of phenolaralkyl resin to epoxy resin, the active hydrogen of the curing agent is present in the epoxy resin at 0.5-1.5 equivalents, preferably 0.8-1.2 equivalents, to 1 equivalent of the epoxy group. Use a curing agent to

In the present invention, in the preparation of various curing agents using phenol aralkyl resins, inorganic fillers and various additives may be added as necessary. The properties of the phenol aralkyl resin as the curing agent can be exhibited even when these various additives are present, so that a resin composition having excellent properties can be obtained.

Useful inorganic fillers include powders such as silica, alumina, silicon nitride, silicon carbide, talc, calcium silicate, clay, and titanium white; And fibers such as glass fibers and carbon fibers, and fillers such as crystalline silica and / or fused silica are preferred in terms of thermal expansion coefficient and thermal conductivity, and spherical fillers or mixtures of spherical and amorphous fillers may be used to form the resin composition. It is desirable in view of flowability in processing.

The usage-amount of an inorganic filler is 100-900 weight part with respect to a total of 100 weight part of an epoxy resin and a hardening | curing agent, and 200-600 weight part is preferable.

The inorganic filler is preferably used in combination with a coupling agent in order to improve adhesion to the resin and to improve mechanical strength and heat resistance, and the coupling agent that can be used is silane-based, titanic acid-based, aluminum-based and zirco-aluminum. It is preferable to use a silane coupling agent and a silane coupling agent, and a silane coupling agent having a functional group reacting with an epoxy resin is particularly preferable.

Examples of the silane coupling agent that can react with the epoxy resin include vinyltrimethoxysilanevinyl-triethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, and 3-amino propyl. Triethoxysilane, 3-anilinopropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3,4-epoxycyclohexyl) -ethyl Trimethoxysilane, 3-methacryloxypropyltrimethoxysilane and 3-mercaptopropyltrimethoxysilane.

It is preferable to use these silane coupling agents individually or in combination, and to adsorb | suck or adhere to the surface of an inorganic filler previously.

It is preferable to use a curing accelerator when curing the resin composition of the present invention. Representative accelerators include 2-methylimidazole, 2-methyl-4-ethylimidazole and 2-heptadecyl. Imidazoles such as midazoles; Amines such as triethanolamine, triethylenediamine and N-ethyl morpholine; Organic phosphines such as tributyl phosphine, triphenyl phosphine and tritolyl phosphine; Tetraphenylborate such as tetraphenylphosphonium tetraphenylborate and triethylammonium tetraphenylborate; And 1,8-diazo-bicyclo (5,4,0) undecene-7 and its derivatives.

The curing accelerator may be used alone or as a mixture, and the use range of these accelerators is 0.01 to 10 parts by weight based on 100 parts by weight of the total of the epoxy resin and the curing agent.

The resin composition is, if necessary, release agents such as fatty acids, fatty acid salts and waxes; A molding material can be prepared by mixing with a colorant such as carbon black and silicon oil of various forms.

Hereinafter, the present invention will be described in detail through synthesis examples and examples, but these synthesis examples and examples do not limit the scope of the present invention.

Synthesis Example 1

In a reaction vessel equipped with a stirrer, a thermometer, an azeotropic trap and a reflux condenser, 249 g (1.5 mol) of α, α'-dimethoxy-p-xylene, 1080 g (7.5 mol) of α-naphthol and 0.67 g (0.05 methanesulfonic acid) %) And the mixture is reacted for 4 hours with stirring at 150-160 ° C. The generated methanol is continuously trapped and removed from the reaction system. After completion of the reaction, unreacted naphthol was distilled off under reduced pressure to obtain 470 g of α-naphthol aralkyl resin of formula (I). As a result of resin composition (area%) by high performance liquid chromatography, 61.5% when n = 0 (compound when n = 0 in Formula I)), 18.2% when n = 1, 8.2% when n = 2 and n3 11.6%. The hydroxy equivalent of the resin is 207.2 g / eg and the softening point is 72 ° C.

Synthesis Example 2

In a reaction vessel equipped with a stirrer, a thermometer, an azeotropic separation trap and a reflux condenser, 207.3 g (1.5 mol) of α, α'-dihydroxy-p-xylene, 2160 g (15 mol) of β-naphthol and 1.18 g of methanesulfonic acid (0.05%) is charged and the mixture is reacted for 4 hours with stirring at 150-160 ° C. The generated methanol is continuously trapped and removed from the reaction system.

After completion of the reaction, unreacted naphthol was distilled off under reduced pressure to obtain 438 g of β-naphthol aralkyl resin of formula (I). As a result of the resin composition (area%) by high performance liquid chromatography, 83.4% when the compound is n = 0 in n = 0 (Formula I), 9.2% when n = 1, 4.6% when n = 2, and 2.8 when n3. %to be. The hydroxy equivalent of the resin is 202.6 g / eq and the softening point is 42 ° C.

Synthesis Example 3

In a reaction vessel equipped with a stirrer, a thermometer, an azeotropic trap and a reflux condenser, 249 g (1.5 mol) of α, α'-dimethoxy-p-xylene, 1275 g (7.5 mol) of 0-phenylphenol and 7.62 g of methanesulfonic acid ( 0.05%) and the mixture is reacted for 4 hours with stirring at 150-160 ° C. The generated methanol is continuously trapped and removed from the reaction system. After completion of the reaction, unreacted 0-phenylphenol was distilled off under reduced pressure to obtain 482 g of 0-phenylphenol aralkyl resin of formula (I). As a result of the resin composition (area%) by high performance liquid chromatography, 61.8% when n = 0 (compound when n = 0 in formula (I)), 17.9% when n = 1, 8.5% when n = 2, and n3 11.8%. The hydroxy equivalent of the resin is 253.2 g / eq and the softening point is 64 ° C.

Synthesis Example 4

Aroma vessel equipped with a stirrer, thermometer, azeotropic separation trap and reflux condenser, 207.3 g (1.5 mol) of α, α'-dihydroxy-p-xylene, 2550 g (15 mol) of p-phenylphenol and 1.38 methanesulfonic acid Charge g (0.05%) and react the mixture for 4 hours with stirring at 150-160 ° C. The generated methanol is continuously trapped and removed from the reaction system. After completion of the reaction, unreacted p-phenylphenol was distilled off under reduced pressure to obtain 453 g of p-phenylphenol aralkyl resin of formula (I). Results of resin composition (area%) by high performance liquid chromatography: 83.6% when n = 0 (compound when n = 0 in formula (I)), 3.4% when n = 1, 4.1% when n = 2, and n3 2.9%. The hydroxy equivalent of the resin is 248.6 g / eq and the softening point is 42 ° C.

The present invention relates to an epoxy resin composition containing a low molecular weight phenol aralkyl resin.

The low molecular weight phenol aralkyl resin used in the present invention may be used as a general phenolic resin to produce a thermosetting resin composition in combination with hexamine, and may also be used as an epoxy resin raw material, a curing agent, and additives of various resins.

In particular, when used as a curing agent for epoxy resins, the obtained epoxy resins are excellent in heat resistance, impact resistance, cracking resistance and moisture resistance, and have excellent workability and can be produced by various means such as casting, adhesion, lamination and molding. In particular, the composition is suitable as a sealing material for semiconductor integrated circuits (IC).

Resin obtained by the synthesis example 1-4 is used as a hardening | curing agent of an epoxy resin. Bis- (4-hydroxyphenyl) methane (bisphenol-F) type epoxy resin, EPIKOTE 807 (trade name, Yuka Shell Epoxy Co.), is mixed with a curing agent under the conditions shown in Table 1.

The properties of the product were tested and the results are shown in Table 1.

The characteristics shown in Tables 1, 2 and 3 are measured by the following method.

Heat Deflection Temperature (HDT): JISK-8207

Glass transition temperature (Tg): measured by TMA method, Shimadzu TMA-System DT-30

Flexural Strength, Flexibility and Elongation: JISK-7113

Boiling water absorption (D-2 / 100); The weight increase after soaking in boiling water at 100 ° C. for 2 hours is measured.

Water Absorption (%): Weight increase after standing in a constant temperature and humidity chamber for 168 hours at 65 ° C and 95% RH.

Comparative Example 1

The same procedure as in Examples 1 to 4 was carried out except that the resin obtained in Synthesis Example 1-4 was replaced with phenol novolak resin and BRG558 (trade name, manufactured by Showa Kobunshi Co.).

The results are shown in Table 1.

Examples 5-16 and 17-28

As a hardening | curing agent, the naphthol aralkyl resin obtained by the synthesis examples 1 and 2 is used individually or in combination with another hardening | curing agent. These aralkyl resins are mixed with various epoxy resins shown in Table 2, and 1 part by weight of 2-undecylimidazole is further added as a curing accelerator.

The mixture is melt kneaded at 120 ° C. and cured at 145 ° C. for 2 hours and at 170 ° C. for 2.5 hours. Physical properties of the obtained cured product were measured, and the results are shown in Table 2.

Using the phenylphenol aralkyl resins obtained in Synthesis Examples 3 and 4 as the curing agent, the same process as described above was carried out to obtain a cured product. The properties of the cured product were measured and the results are shown in Table 3.

In Tables 2 and 3, the following epoxy resins are used.

(A) Epoxy resins derived from 2,2-bis (4-hydroxyphenyl) propane having an epoxy equivalent of 189, EPIKOTE 828 (trade name, Dow Chemical Co.)

(B) Epoxy resins derived from phenol-novolak resins having an epoxy equivalent of 179, DEN-431 (trade name, Nippon Kayaku Co.)

(C) Epoxy resin derived from 0-cresol noborac resin, epoxy equivalent of 218, EOCN-1029 (trade name, Ciba-Geigy Co.)

(D) An epoxy resin derived from 4,4'-methylenedianiline having an epoxy equivalent of 122.

ARALDITE MY-720 (trade name, Ciba-Geigy Co.)

(E) Epoxidized Phenol Aralkyl Resin Prepared by the Following Process

To a reaction vessel equipped with a stirrer, a thermometer, an azeotropic trap and a reflux condenser, 250 g (1.5 mol) of α, α'-dimethoxy-P-xylene, 847 g (9 mol) of phenol and 1.1 g of P-toluenesulfonic acid were charged. And, the mixture is reacted for 3 hours while stirring at 130 ~ 150 ℃.

The generated methanol is continuously trapped and removed from the reaction system. After completion of the reaction, unreacted phenol was distilled off under reduced pressure to obtain 393 g of phenol aralkyl resin.

As a result of the resin composition (area%) by high performance liquid chromatography, it was 60.3% when n = 0, 24.3% when n = 1, 9.2% when n = 2, and 6.2% when n3.

Into a reaction vessel equipped with a stirrer, an azeotropic separation trap and a dropping funnel, 393 g of the resin obtained above and 1100 g (11.9 mol) of epihalohydrin are charged. The mixture is heated to 115-119 ° C. and 275 g of 40% aqueous sodium hydroxide solution is added dropwise over 4 hours while maintaining the mixture at the same temperature. The azeotropic epihalohydrin is then returned to the reaction vessel and the separated water is removed from the system. After completion of the dropping, the reaction is terminated when water separation stops.

Thereafter, distillation under reduced pressure removes excess epihalohydrin. The reaction product is dissolved in 1500 g of methyl isobutyl ketone (MIBK) and excess sodium hydroxide and sodium chloride by-products are filtered off. The product was washed twice with 300 g of water, distilled under reduced pressure to remove MIBK to obtain 465 g of epoxy resin as a yellow oil having an epoxy equivalent of 227 g / eg.

(F) Epoxidized resorcinol-aralkyl resin prepared by the following process.

In a reaction vessel equipped with a stirrer, a thermometer, an azeotropic separation trap, and a reflux condenser, 150 g (1.5 mol) of α, α'-dimethoxy-P-xylene, 1650 g (15 mol) of resorcinol and 0.2 g of methane sulfone Charged and the mixture was reacted for 3 hours with stirring at 130-150 ° C.

The generated methanol is continuously trapped and removed from the reaction system. After completion of the reaction, unreacted resorcinol was distilled off under reduced pressure to obtain 452 g of resorcinol aralkyl resin. As a result of the resin composition (area%) by high performance liquid chromatography, n = 63.3%, n = 1 24.3%, n = 2, 9.2%, and n 3, 6.0%.

Into a reaction vessel equipped with a stirrer, an azeotropic separation trap and a dropping funnel, 452 g of the resin obtained above and 1100 g (11.9 mol) of epihalohydrin are charged. The mixture is heated to 115-119c, and 275 g of 40% aqueous sodium hydroxide solution is added dropwise over 4 hours while maintaining the mixture at the same temperature.

Subsequently, the azeotropic epihalohydrin is returned to the reaction vessel, and the separated water is removed from the system. After completion of the dropping, the reaction is terminated when water separation stops.

Then, distillation under reduced pressure removes excess epihalohydrin. The reaction product is dissolved in 1500 g of ethyl acetate and excess sodium hydroxide and sodium chloride by-products are filtered off.

The product was washed twice with 300 g of water, distilled under reduced pressure to remove ethyl acetate to obtain 546 g of epoxy resin as a yellow oil having an epoxy equivalent of 159 g / eg.

Comparative Example 2-4

The same process as in Example 17 was carried out using an epoxy resin (A), (C) or (F) and a phenol novolak resin or 4,4'-diaminodiphenyl sulfone (DDS) as a curing agent. The physical properties of the obtained product were measured and the results are shown in Table 3.

Examples 29-40

Resin obtained by the synthesis examples 1 and 2 is used individually or in combination with a phenol novolak resin and EOCN-1020 (trade name, Nippon Kayaku Co.) as a hardening | curing agent for 0-cresol novolak-type epoxy resins.

Inorganic fillers and other additives were combined as shown in Table 4.

The resulting mixture is cast into a mold and cured. The properties of the cast product were specified and the results are shown in Table 4.

By carrying out the same process as above using the resin obtained by the synthesis examples 3 and 4, the hardened | cured product like the ratio shown in Table 5 is obtained. The physical properties of these products were measured, and the results are shown in Table 5.

The test pieces for measuring the physical properties shown in Tables 4 and 5 were prepared by transfer molding the resin composition at 180 ° C. under 30 Kg / cm 2 for 3 minutes.

A semiconductor test apparatus is manufactured by installing a test element of 10 × 100 mm in an element fixing part of a lead frame for use in a flat package semiconductor device, and transferring the mold at 30 ° C./cm 2 at 180 ° C. for 3 minutes.

These test pieces are cured after 6 hours at 180 ° C. before the test.

Comparative Examples 5-6

Except for using phenol novolak resin alone as a curing agent, the same steps as in Example 29-40 are carried out. The properties of the cured product were measured and the results are shown in Tables 4 and 5.

Test the property in the following way:

Glass transition temperature: TMA method

Measured with Shimadzu TMA-System DT-30

Flexural Strength and Flexure Ratio: JIS K-6911

Tensile Strength, Elastic Modulus and Elongation: JIS K-7113

Water Absorption (%): The increase in weight after standing for 168 hours at 65 ° C and 95% RH in a thermo-hygrostat is measured.

V.S.P Test: Leave the semiconductor test apparatus for 168 hours at 65 ° C, 95% RH in a thermo-hygrostat and immediately soak in FLUORINERT Liguid FC-70 (trade name, Sumitomo 3M Co.). The number of cracked semiconductor devices in the package resin is counted. The results are shown in fractional form, the numerator representing the number of cracked units and the denominator the total number of units used in the test.

Example 41

The resin obtained in Synthesis Example 1 is melt kneaded with hexamethylenetetramine under the condition shown in Table 6. The resulting cured product is subjected to differential thermal analysis and thermogravimetric analysis. The results are shown in Table 6.

Comparative Example 7

The same process as in Example 41 was carried out except for using phenol novolak resin and BRG-558 (trade name, Showa Kobunshi, Co.). The obtained cured product was subjected to differential thermal analysis and thermogravimetric analysis, and the results are shown in Table 6.

The epoxy resin composition obtained by using naphthol aralkyl resin as the curing component is excellent in properties such as heat resistance, impact resistance, cracking resistance, and moisture resistance, and is very useful as various matrix resins.

TABLE 1

Note: 1) Epoxy equivalent

2) hydroxy equivalent

3) Heat deflection temperature

4) Glass transition temperature

5) Boiling 2 hours at 100 ℃

TABLE 2

In Tables 2 and 3,

Epoxy resin (A): Epikote 828 (trade name, UKa Shell Co.) Epoxy equivalent 189

Epoxy resin (B): DEN-431 (trade name, Dow Chem. Cc.) Epoxy equivalent 179

Epoxy resin (C): EOCN-102 (trade name, Nippon Kayaku Co.) Epoxy Equivalent 218

Epoxy Resin (D): Araldite MY-720 (trade name, Ciba-Geigyud) Epoxy Equivalent 122

Epoxy resin (E): epoxidized phenol aralkyl resin (manufacturing) epoxy equivalent 227

Epoxy Resin (F): Epoxidized Resorcinol Aralkyl Resin (Manufacturing) Epoxy Equivalent 159

BRG # 588: Phenolic Novolak Resin (produced by showa Kovunshi Co.) Epoxy equivalent 104

DDS: 4,4'-diamino diphenylsulfone

For all applications, one part of 2-undecylimidazole (C ¹¹ Z) is used as curing agent.

TABLE 4

TABLE 5

In Tables 4 and 5

Epoxy Resin: 0-Cresol Novolac Epoxy Resin, EOCN-102S (trade name, Nippon Kayaku Co.)

Novolak-type phenol resin: PN-80 (trade name, Nippon Kayaku Co.)

Inorganic springs: 50/50 weight mixture of spherical molten silica, Harimic S-CO (trade name, Micron Co.) and amorphous molten silica, Fuserex RD-8 (trade name, Tatsumori Co.)

Silane coupling agent: SZ-6083 (trade name, Toray Dow-Corning Silicone Co.)

TABLE 6

Note: 1) Air flow rate: 100ml / min Temperature rise rate: 5 ℃ / min

Claims (11)

Formula (I) (Where X is or Is a divalent group, n is an integer of 0 to 10), and a curing agent component and epoxy containing a low molecular weight phenolaralkyl resin having a softening point of 100 ° C. or less in an amount of 10 to 100% by weight based on the total amount of the curing agent component. Epoxy resin composition consisting of a resin. The phenol aralkyl resin of claim 1, wherein the phenol aralkyl resin is formula (II) (Wherein n is an integer of 0 to 10) and an epoxy resin composition characterized by being a low molecular weight phenylphenol aralkyl resin having a softening point of 100 ° C. or less. The phenol aralkyl resin of claim 1, wherein the phenol aralkyl resin is formula (III) (Wherein n is an integer of 0 to 10) and an epoxy resin composition characterized in that it is a low molecular weight naphthol aralkyl resin having a softening point of 100 ° C. or less, The epoxy resin composition according to claim 1, 2 or 3, wherein the epoxy resin is an epoxy compound obtained by reacting 2,2-bis (4-hydroxyphenyl) propane with epihalohydrin. The epoxy resin according to claim 1, 2 or 3, wherein the epoxy resin is an epoxy compound obtained by reacting 2,2-bis (3,5-dibromo-4-hydroxyphenyl) propane with epihalohydrin. Epoxy resin composition, characterized in that. The epoxy resin composition according to claim 1, 2 or 3, wherein the epoxy resin is an epoxy compound obtained by reacting bis (4-hydroxyphenyl) methane with epihalohydrin. The epoxy resin composition according to claim 1, 2 or 3, wherein the epoxy resin is an epoxy compound obtained by reacting phenol novolak and epihalohydrin. The epoxy resin composition according to claim 1, 2 or 3, wherein the epoxy resin is an epoxy compound obtained by reacting 0-cresol novolak with epihalohydrin. The epoxy resin composition according to claim 1, 2 or 3, wherein the epoxy resin is an epoxy compound obtained by reacting 4,4-methylenedianiline and epihalohydrin. The compound according to claim 1, 2 or 3, wherein the epoxy compound is of formula (V) N is an multifunctional epoxy compound obtained by reacting phenol aralkyl resin and epihalohydrin represented by (wherein n is an integer of 0 to 10). The epoxy resin according to claim 1, 2 or 3, wherein the epoxy resin is formula (VI) Epoxy resin composition, characterized in that the polyfunctional epoxy compound obtained by reacting resorcinol aralkyl resin and epihalohydrin represented by.