JP4667753B2 - Epoxy resin production method, epoxy resin composition and cured product - Google Patents

Description

  The present invention relates to an epoxy resin, an epoxy resin composition, and a cured product thereof useful for sealing electric and electronic parts, circuit board materials, adhesives, paints, and the like.

  In recent years, particularly with the advancement of the advanced material field, development of higher performance base resins has been demanded. For example, in the field of semiconductor encapsulation, the problem of package cracking has become serious due to the thinning and large area of packages corresponding to recent high-density mounting and the spread of surface mounting methods. As a base resin, improvement in moisture resistance, heat resistance, adhesion to a metal substrate, and the like is strongly demanded. More recently, from the viewpoint of reducing environmental impact, there has been a movement to eliminate halogen-based flame retardants, and there is a demand for base resins that are more excellent in flame retardancy.

  However, no conventionally known epoxy resins satisfy these requirements. For example, Patent Documents 1 and 2 propose naphthalene-type epoxy resins that are excellent in low hygroscopicity and high heat resistance. However, many epoxy resins having a naphthalene structure have a high viscosity and are easy to mold. There were inferior drawbacks.

JP-A-3-717 Japanese Patent Laid-Open No. 3-90075

  Therefore, the object of the present invention is excellent in moisture resistance, heat resistance, flame retardancy, adhesion to a metal substrate and the like, and useful for applications such as lamination, molding, casting, adhesion, etc. having good moldability. An object of the present invention is to provide an epoxy resin, a production method thereof, an epoxy resin composition using them, and a cured product thereof.

（但し、ｎは平均値で１．１から４．０の数を示す。）で表されるナフトール樹脂１００重量部に対して、下記一般式（２）、

（但し、Ｒ₁、Ｒ₂は水素原子又は炭素数１〜８の炭化水素基を示し、Ｘは直接結合又はメチレン基を示す。）で表されるビスフェノール化合物１０〜６０重量部を混合したのち、エピクロロヒドリンと反応させることを特徴とするエポキシ樹脂の製造方法である。
ここで、ビスフェノール化合物としては、４，４'−ジヒドロキシビフェニル又は３，３'，５，５'−テトラメチル−４，４'−ジヒドロキシジフェニルメタンが好ましく例示される。 That is, the present invention provides the following general formula (1),

(Where n is an average value and represents a number from 1.1 to 4.0), with respect to 100 parts by weight of naphthol resin, the following general formula (2),

(However, R ₁ and R ₂ represent a hydrogen atom or a hydrocarbon group having 1 to 8 carbon atoms, and X represents a direct bond or a methylene group. ) After mixing 10 to 60 parts by weight of a bisphenol compound represented by And an epoxy resin production method characterized by reacting with epichlorohydrin.
Here, as the bisphenol compound, 4,4′-dihydroxybiphenyl or 3,3 ′, 5,5′-tetramethyl-4,4′-dihydroxydiphenylmethane is preferably exemplified.

  Moreover, this invention is an epoxy resin obtained by the manufacturing method of the said epoxy resin. This epoxy resin preferably has a softening point of 50 to 110 ° C. Furthermore, this invention is the epoxy resin composition formed by mix | blending the said epoxy resin and a hardening | curing agent, and an epoxy resin hardened | cured material formed by hardening | curing this.

Hereinafter, the present invention will be described in detail.
The epoxy resin of the present invention can be obtained by reacting a mixture of the naphthol resin represented by the general formula (1) and the bisphenol compound represented by the general formula (2) with epichlorohydrin. Even if the epoxidized product of naphthol resin has a high viscosity, an epoxy resin excellent in fluidity can be obtained by combining with an epoxidized product of a low-viscosity bisphenol compound. The mixing ratio of the naphthol resin and the bisphenol compound is in the range of 10 to 60 parts by weight, preferably in the range of 15 to 40 parts by weight with respect to 100 parts by weight of the naphthol resin. If it is less than this, the improvement effect of fluidity | liquidity is small, and when more than this, heat resistance, moisture resistance, and a flame retardance will fall.

  The naphthol resin used in the present invention has a structure represented by the above general formula (1), wherein the repeating unit n is an average value of 1.1 to 4.0, preferably 1.2 to 3.0. If it is smaller than this, the heat resistance and moisture resistance are lowered, and if it is larger than this, the viscosity is increased and the moldability is lowered.

  The softening point range of the naphthol resin is usually 50 to 150 ° C, preferably 60 to 120 ° C, and more preferably 60 to 90 ° C. When it is lower than this, the heat resistance is lowered, and when it is higher than this, the fluidity is lowered. The hydroxyl equivalent is usually in the range of 180 to 240, preferably in the range of 190 to 230.

  The naphthol resin used in the present invention can be obtained, for example, by reacting naphthols with an aromatic crosslinking agent such as p-xylylene glycol in the presence of an acidic catalyst. In this reaction, 0.1 to 0.9 mol of an aromatic crosslinking agent is usually used for 1 mol of naphthols. After completion of the reaction, excess naphthols are usually removed out of the system by a method such as vacuum distillation. Further, without removing excess naphthols out of the system, for example, as described in JP-A-5-148333, by reacting the remaining naphthols with formaldehyde such as paraformaldehyde, A method of remaining in the system as a dimer and apparently reducing the remaining naphthols may be used. Naphthol is usually removed until the amount remaining in the naphthol resin is 5 wt% or less, preferably 2 wt% or less.

  The naphthols used in producing the naphthol resin used in the present invention include 1-naphthol and 2-naphthol, and these may be used alone or as a mixture. Examples of the aromatic crosslinking agent include p-xylylene glycol, 1,4-dichloromethylbenzene, 1,4-dimethoxymethylbenzene, 1,4-diethoxymethylbenzene and the like.

The bisphenol compound used in the present invention has a structure represented by the above formula (2). In the formula, R ₁ and R ₂ are hydrogen atom, methyl group, ethyl group, n-propyl group, isopropyl group, allyl group, propargyl group, butyl group, n-amyl group, sec-amyl group, tert-amyl group, Although it is a C1-C8 hydrocarbon group, such as a cyclohexyl group, a phenyl group, or a benzyl group, Preferably they are a hydrogen atom or a methyl group.
X represents a direct bond, an ether group, a sulfide group, a sulfone group, a ketone group, a methylene group or an isopropylidene group, preferably a direct bond or a methylene group. Specific examples of the bisphenol compound include 4,4′-dihydroxybiphenyl, 3,3 ′, 5,5′-tetramethyl-4,4′-dihydroxybiphenyl, 4,4′-dihydroxydiphenylmethane, and 3,3′-. Dimethyl-4,4′-dihydroxydiphenylmethane, 3,3 ′, 5,5′-tetramethyl-4,4′-dihydroxydiphenylmethane, 4,4′-dihydroxydiphenyl ether, 3,3 ′, 5,5′-tetra Methyl-4,4′-dihydroxydiphenyl ether, 4,4′-dihydroxydiphenyl sulfide, 3,3′-dimethyl-4,4′-dihydroxydiphenyl sulfide, 3,3 ′, 5,5′-tetramethyl-4, 4'-dihydroxydiphenyl sulfide, 4,4'-dihydroxydiphenyl sulfone, 3,3 ', 5,5'-tetramethyl-4 4'-dihydroxydiphenyl sulfone, 4,4'-dihydroxydiphenyl ketone, bisphenol A, and the like.

  The epoxy resin of the present invention can be produced by reacting a mixture of the naphthol resin of the general formula (1) and the bisphenol compound of the general formula (2) with epichlorohydrin. The same can be done.

  For example, after the above mixture is dissolved in excess epichlorohydrin, in the presence of an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide, 20 to 150 ° C., preferably 30 to 80 ° C. in the range of 1 to 10 The method of making it react for time is mentioned. The amount of the alkali metal hydroxide used in this case is in the range of 0.8 to 1.2 mol, preferably 0.9 to 1.0 mol, with respect to 1 mol in total of the naphthol resin and the hydroxyl group of the bisphenol compound. It is. Epichlorohydrin is used in an excess amount relative to the total number of hydroxyl groups in the naphthol resin and bisphenol compound, but is usually in the range of 1.5 to 30 mol, preferably 2 to 15 mol, based on 1 mol of the total hydroxyl group. It is.

  In this reaction, a solvent such as dimethyl sulfoxide, diethylene glycol dimethyl ether, or triethylene glycol dimethyl ether may coexist.

  After completion of the reaction, excess epichlorohydrin is distilled off, the residue is dissolved in a solvent such as toluene and methyl isobutyl ketone, filtered, washed with water to remove inorganic salts, and then the target epoxy resin is distilled off. Can be obtained.

  The epoxy resin of the present invention is obtained by the above-described production method, and is mainly one in which the naphthol resin represented by the general formulas (1) and (2) and the hydroxyl group in the bisphenol compound are changed to a glycidyl ether group. (Preferably 90 wt% or more), and a small amount of oligomers formed by partial cleavage of epoxy groups. Therefore, the epoxy resin of the present invention is also a mixture of an epoxy resin produced from a naphthol resin represented by the general formulas (1) and (2) and a bisphenol compound. The epoxy resin preferably has a softening point of 50 to 110 ° C.

  The epoxy resin of this invention can take the method of making the epoxy resin obtained by the said reaction contact a basic substance further in order to reduce hydrolysable chlorine. This reaction is usually carried out in a solvent such as toluene, xylene, n-butanol, methyl isobutyl ketone. Examples of the basic substance include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide.

  The amount of hydrolyzable chlorine in the epoxy resin of the present invention is preferably small from the viewpoint of improving the reliability of the electronic component to be sealed. Although it does not specifically limit, 1000 ppm or less is preferable, More preferably, it is 500 ppm or less. In addition, the hydrolyzable chlorine as used in the field of this invention means the value measured by the following method. That is, 0.5 g of sample was dissolved in 30 ml of dioxane, 1N-KOH, 10 ml was added, and the mixture was boiled and refluxed for 30 minutes, cooled to room temperature, further added with 100 ml of 80% acetone water, and potentiometric titration with 0.002N-AgNO3 aqueous solution. Is a value obtained by performing

  The epoxy resin composition of this invention consists of an epoxy resin and a hardening | curing agent, and mix | blends the epoxy resin of this invention as an essential component as an epoxy resin component.

  In addition to the epoxy resin of the present invention, a normal epoxy resin having two or more epoxy groups in the molecule may be blended with the epoxy resin composition of the present invention. Examples of such an epoxy resin include divalent phenols such as bisphenol A, bisphenol F, bisphenol S, fluorene bisphenol, 4,4′-biphenol, 2,2′-biphenol, hydroquinone, and resorcin, tris- (4 -Hydroxyphenyl) methane, 1,1,2,2-tetrakis (4-hydroxyphenyl) ethane, phenol novolak, trivalent or higher phenols such as o-cresol novolak, and halogenated bisphenols such as tetrabromobisphenol A Examples thereof include glycidyl etherification products derived. These epoxy resins may be used alone or in combination of two or more. These blending amounts may be in a range that does not impair the object of the present invention, but are usually within 50% by weight with respect to the epoxy resin of the present invention.

  As the curing agent used in the epoxy resin composition of the present invention, any one generally known as an epoxy resin curing agent can be used. Examples include dicyandiamide, polyhydric phenols, acid anhydrides, aromatic and aliphatic amines.

  Specifically, as polyhydric phenols, for example, bisphenol A, bisphenol F, bisphenol S, fluorene bisphenol, 4,4′-biphenol, 2,2′-biphenol, hydroquinone, resorcin, catechol, naphthalenediols Divalent phenols such as tris- (4-hydroxyphenyl) methane, 1,1,2,2-tetrakis (4-hydroxyphenyl) ethane, phenol novolac, o-cresol novolak, naphthol novolak, polyvinylphenol, etc. Representative trihydric or higher phenols, further phenols, naphthols, bisphenol A, bisphenol F, bisphenol S, fluorene bisphenol, 4,4'-biphenol, 2,2'-biphenol, hydro Divalent phenols such as non-resorcin, catechol, naphthalenediol and formaldehyde, acetaldehyde, benzaldehyde, p-hydroxybenzaldehyde, p-xylylene glycol, p-xylylene glycol dimethyl ether, divinylbenzene, diisopropenylbenzene, dimethoxy Examples thereof include polyhydric phenolic compounds synthesized by a reaction with a crosslinking agent such as methylbiphenyls, divinylbiphenyl, diisopropenylbiphenyls, and the like.

  The softening point range of the phenolic curing agent is preferably 40 to 150 ° C, more preferably 50 to 120 ° C. If it is lower than this, there is a problem of blocking during storage, and if it is higher than this, there is a problem in kneadability and moldability during preparation of the epoxy resin composition. Further, the melt viscosity at 150 ° C. is preferably 20 poises or less, more preferably 5 poises or less. When higher than this, there exists a problem in the kneadability at the time of preparation of an epoxy resin composition, and a moldability.

  Examples of the acid anhydride include phthalic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, methyl hymic anhydride, nadic anhydride, and trimellitic anhydride.

  Examples of amines include aromatic amines such as 4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenylpropane, 4,4′-diaminodiphenylsulfone, m-phenylenediamine, and p-xylylenediamine, ethylenediamine, There are aliphatic amines such as hexamethylenediamine, diethylenetriamine, and triethylenetetramine.

  In the resin composition of the present invention, one or more of these curing agents can be mixed and used.

  The epoxy resin composition of the present invention is useful for sealing. Examples of the inorganic filler compounded in the epoxy resin composition for sealing include silica, alumina, zircon, calcium silicate, calcium carbonate, silicon carbide, silicon nitride, boron nitride, zirconia, fosterite, steatite, spinel, mullite. 1 type or 2 or more types such as titania, and the form includes powder, spherical beads and the like. Among these, spherical fused silica is preferable from the viewpoint of increasing the filling of the inorganic filler. Usually, silica is used in combination with those having several kinds of particle size distributions. The range of the average particle diameter of the silica to be combined is preferably 0.5 to 100 μm.

  The blending amount of the inorganic filler is 75% by weight or more, preferably 80% by weight or more of the entire epoxy resin composition. If it is less than this, the effect of improving solder heat resistance and flame retardancy is small.

  Conventionally known curing accelerators such as amines, imidazoles, organic phosphines, Lewis acids and the like may be added to the epoxy resin composition of the present invention. Specifically, tertiary amines such as 1,8-diazabicyclo (5,4,0) undecene-7, triethylenediamine, benzyldimethylamine, triethanolamine, dimethylaminoethanol, tris (dimethylaminomethyl) phenol, Organic compounds such as 2-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, imidazoles such as 2-heptadecylimidazole, tributylphosphine, methyldiphenylphosphine, triphenylphosphine, diphenylphosphine, and phenylphosphine Tetra-substituted phosphonium such as phosphines, tetraphenylphosphonium / tetraphenylborate, tetraphenylphosphonium / ethyltriphenylborate, tetrabutylphosphonium / tetrabutylborate · Tetra-substituted borate, 2-ethyl-4-methylimidazole · tetraphenyl borate, etc. tetraphenyl boron salts such as N- methylmorpholine tetraphenylborate and the like. As addition amount, it is 0.2-10 weight part normally with respect to 100 weight part of epoxy resins.

  The epoxy resin composition of the present invention includes a release agent such as carnauba wax and ester wax, a coupling agent such as epoxy silane, amino silane, ureido silane, vinyl silane, alkyl silane, organic titanate, and aluminum alcoholate, carbon A colorant such as black, a flame retardant aid such as antimony trioxide, a low stress agent such as silicone oil, a lubricant such as a higher fatty acid and a higher fatty acid metal salt may be blended.

  Generally, an epoxy suitable for sealing electronic components is prepared by thoroughly mixing the above raw materials in a predetermined blending amount with a mixer or the like, then kneading with a mixing roll, an extruder, etc., cooling and pulverizing. A resin composition can be prepared.

  As a method for sealing an electronic component using this epoxy resin composition, a low-pressure transfer molding method is most common, but an injection molding method or a compression molding method is also possible.

  The epoxy resin composition of the present invention is excellent in moisture resistance, heat resistance, flame retardancy, adhesion to a metal substrate, etc., and has good moldability, and is used as a sealing material for electronic and electrical parts. It can be preferably used. In addition, the cured epoxy resin of the present invention and the electronic component sealed with the epoxy resin are excellent in heat resistance and electrical insulation.

  Hereinafter, the present invention will be described more specifically with reference to examples.

Synthesis example 1 (Synthesis example of naphthol resin)
To a 2000 ml 4-neck flask was charged 1000 g (6.94 mol) of 2-naphthol, 144 g (1.04 mol) of paraxylylene glycol and 550 g of toluene, and then 0.44 g of p-toluenesulfonic acid was added as a catalyst. The mixture was heated with stirring and reacted at 130 ° C. for 2 hours, and the generated water was removed from the system. After the reaction, the reaction mixture was neutralized with sodium carbonate, and unreacted 2-naphthol was distilled off under reduced pressure to obtain 380 g of a brown resin. The obtained naphthol resin had a hydroxyl group equivalent of 205, a softening point of 97 ° C., and a melt viscosity at 150 ° C. of 0.31 Pa · s.

Synthesis Example 2 (Synthesis example of naphthol resin)
To a 2000 ml four-necked flask was charged 564 g of 2-naphthol (3.92 mol) and 200 g (1.46 mol) of paraxylylene glycol, and then 0.68 g of p-toluenesulfonic acid was added as a catalyst and stirred. The temperature was raised while the reaction was carried out at 150 ° C. for 2 hours, and the produced water was removed from the system. After the reaction, neutralization was performed with sodium carbonate. After maintaining at 150 ° C., 12.6 hours after removing 32.6 g (1.0 mol) of 92% paraformaldehyde and removing generated water out of the system, 706 g of a brown resin was obtained. The obtained naphthol resin had a hydroxyl group equivalent of 205, a softening point of 105 ° C., and a melt viscosity at 150 ° C. of 1.05 Pa · s.

Example 1
170 g of the naphthol resin obtained in Synthesis Example 2 and 30 g of 3,3 ′, 5,5′-tetramethyl-4,4′-dihydroxydiphenylmethane were dissolved in 590 g of epichlorohydrin and 88.6 g of diethylene glycol dimethyl ether. Under reduced pressure (about 140 mmHg), 86.8 g of 48% aqueous sodium hydroxide solution was added dropwise at 65 ° C. over 4 hours. During this time, the generated water was removed from the system by azeotropy with epichlorohydrin, and the distilled epichlorohydrin was returned to the system. After completion of the dropwise addition, the reaction was continued for another 30 minutes. Then, the epichlorohydrin was distilled off except the salt produced | generated by water washing, and the crude epoxy resin was obtained. The obtained crude epoxy resin was dissolved in 760 ml of methyl isobutyl ketone, then heated to 80 ° C., 17.6 g of 10% sodium hydroxide was added with stirring, and the mixture was reacted for 2 hours. After the reaction, after washing with ion exchange water, methyl isobutyl ketone was distilled off to obtain 234 g of a brown epoxy resin (epoxy resin A). The epoxy equivalent was 248, the softening point was 72 ° C., the melt viscosity at 150 ° C. based on the ICI corn plate method was 0.13 Pa · s, and the hydrolyzable chlorine was 320 ppm. A GPC chart of the obtained resin is shown in FIG. Here, the GPC measurement uses an apparatus: HLC-82A (manufactured by Tosoh Corporation) and a column: TSK-GEL 2000 × 3 and TSK-GEL4000 × 1 (both manufactured by Tosoh Corporation), and a solvent: tetrahydrofuran. Flow rate: 1.0 ml / min, temperature: 38 ° C., detector: RI. Hydrolyzable chlorine is obtained by performing potentiometric titration with a silver nitrate solution of 0.5 g of a resin sample dissolved in 30 ml of 1,4-dioxane and boiled for 30 minutes with 5 ml of 1N KOH / methanol solution. Asked.

Example 2
170 g of naphthol resin obtained in Synthesis Example 2 and 30 g of 4,4′-dihydroxybiphenyl were dissolved in 640 g of epichlorohydrin and 96.0 g of diethylene glycol dimethyl ether, and 48% sodium hydroxide at 65 ° C. under reduced pressure (about 140 mmHg). 94.0 g of an aqueous solution was added dropwise over 4 hours. During this time, the generated water was removed from the system by azeotropy with epichlorohydrin, and the distilled epichlorohydrin was returned to the system. After completion of the dropping, the reaction was continued for another 30 minutes. Then, the epichlorohydrin was distilled off except the salt produced | generated by water washing, and the crude epoxy resin was obtained. The obtained crude epoxy resin was dissolved in 770 ml of methyl isobutyl ketone, then heated to 80 ° C., and 17.8 g of 10% sodium hydroxide was added with stirring to react for 2 hours. After the reaction, after washing with ion exchange water, methyl isobutyl ketone was distilled off to obtain 238 g of brown epoxy resin (epoxy resin B). The epoxy equivalent was 240, the softening point was 91 ° C., the melt viscosity at 150 ° C. based on the ICI cone plate method was 0.10 Pa · s, and the hydrolyzable chlorine was 320 ppm.

Example 3
170 g of naphthol resin obtained in Synthesis Example 1 and 30 g of 4,4′-dihydroxybiphenyl were dissolved in 640 g of epichlorohydrin and 96.0 g of diethylene glycol dimethyl ether, and 48% sodium hydroxide at 65 ° C. under reduced pressure (about 140 mmHg). 94.0 g of an aqueous solution was added dropwise over 4 hours. During this time, the generated water was removed from the system by azeotropy with epichlorohydrin, and the distilled epichlorohydrin was returned to the system. After completion of the dropping, the reaction was continued for another 30 minutes. Then, the epichlorohydrin was distilled off except the salt produced | generated by water washing, and the crude epoxy resin was obtained. The obtained crude epoxy resin was dissolved in 770 ml of methyl isobutyl ketone, then heated to 80 ° C., and 17.8 g of 10% sodium hydroxide was added with stirring to react for 2 hours. After the reaction, washing with ion-exchanged water was performed, and then methyl isobutyl ketone was distilled off to obtain 246 g of a brown epoxy resin (epoxy resin C). Epoxy equivalent was 235, softening point was 86 ° C., melt viscosity at 150 ° C. based on ICI corn plate method was 0.08 Pa · s, and hydrolyzable chlorine was 270 ppm.

Comparative Synthesis Example 1
200 g of the naphthol resin obtained in Synthesis Example 1 was dissolved in 640 g of epichlorohydrin and 96.0 g of diethylene glycol dimethyl ether, and 77.2 g of 48% sodium hydroxide aqueous solution was added over 4 hours at 65 ° C. under reduced pressure (about 140 mmHg). It was dripped. During this time, the generated water was removed from the system by azeotropy with epichlorohydrin, and the distilled epichlorohydrin was returned to the system. After completion of the dropping, the reaction was continued for another 30 minutes. Then, the epichlorohydrin was distilled off except the salt produced | generated by water washing, and the crude epoxy resin was obtained. The obtained crude epoxy resin was dissolved in 770 ml of methyl isobutyl ketone, and then heated to 80 ° C., 21.5 g of 10% sodium hydroxide was added with stirring and reacted for 2 hours. After the reaction, washing with ion-exchanged water was performed, and then methyl isobutyl ketone was distilled off to obtain 237 g of a brown epoxy resin (epoxy resin D). The epoxy equivalent was 283, the softening point was 85 ° C., the melt viscosity at 150 ° C. based on the ICI corn plate method was 0.36 Pa · s, and hydrolyzable chlorine was 340 ppm.

Comparative Synthesis Example 2
Using 200 g of the naphthol resin obtained in Synthesis Example 2, the reaction was performed in the same manner as in Comparative Synthesis Example 1 to obtain 232 g of a brown epoxy resin (Epoxy Resin E). The epoxy equivalent was 281, the softening point was 83 ° C., the melt viscosity at 150 ° C. based on the ICI cone plate method was 0.33 Pa · s, and hydrolyzable chlorine was 380 ppm.

Examples 4-8, Comparative Examples 1-4
Epoxy resins synthesized in Examples 1 to 3 and Comparative Synthesis Examples 1 and 2, o-cresol novolak type epoxy resin (epoxy equivalent 197, softening point 54 ° C., melt viscosity 90 ° C. at 150 ° C .; EOCN-1020, Japan Epoxy resin F), phenol novolak (OH equivalent 104, softening point 46 ° C., melt viscosity 20 mPa · s at 150 ° C .; phenol resin A) and phenol aralkyl resin (OH equivalent 175, softening point 75 ° C., 150 Melt viscosity at ° C. 0.32 Pa · s; MEH-7800S, manufactured by Meiwa Kasei; phenol resin B) , triphenylphosphine as curing accelerator, and γ-glycidoxypropyltrimethoxysilane as silane coupling agent A resin composition was obtained with the formulation shown in Table 1.

  The epoxy resin composition was molded at 175 ° C., post-cured at 175 ° C. for 12 hours to obtain a cured product test piece, and subjected to various physical property measurements. The glass transition point was calculated | required on the conditions of the temperature increase rate of 7 degree-C / min with the thermomechanical measuring apparatus. The bending test was performed by a three-point bending method for high-temperature bending strength and bending elastic modulus at room temperature and 240 ° C. The adhesive strength is a 25 mm × 12.5 mm × 0.5 mm molded product between two copper plates or iron plates, molded at 175 ° C. with a compression molding machine, post-cured at 175 ° C. for 12 hours, and then tensile shear strength Was evaluated. The water absorption rate is obtained when a disc having a diameter of 50 mm and a thickness of 3 mm is formed using this epoxy resin composition, and after post-curing and absorbing moisture for 100 hours under the conditions of 85 ° C. and 85% RH, cracks are generated. The rate is QFP-80pin (14 mm x 20 mm x 2.5 mm, 194 alloy), post-cured, moisture-absorbed for a specified time at 85 ° C and 85% RH, and then immersed in a solder bath at 260 ° C for 10 seconds. Then, the state of the package was observed and determined. The results are summarized in Table 2.

  As a result of the blocking test, the blocking rate after standing for 24 hours at 25 ° C. using a 1 mm pass powder of the epoxy resin composition was expressed in weight%. In addition, the storage stability was expressed as a residual rate of spiral flow after leaving the epoxy resin composition at 25 ° C. for 1 week.

GPC chart of epoxy resin A obtained in Example 1

Claims (6)

The following general formula (1),

(Where n is an average value and represents a number from 1.1 to 4.0), with respect to 100 parts by weight of naphthol resin, the following general formula (2),

(However, R ₁ and R ₂ represent a hydrogen atom or a hydrocarbon group having 1 to 8 carbon atoms, and X represents a direct bond or a methylene group. ) After mixing 10 to 60 parts by weight of a bisphenol compound represented by A method for producing an epoxy resin, characterized by reacting with epichlorohydrin.
  The method for producing an epoxy resin according to claim 1, wherein the bisphenol compound is 4,4'-dihydroxybiphenyl or 3,3 ', 5,5'-tetramethyl-4,4'-dihydroxydiphenylmethane.   The epoxy resin obtained by the manufacturing method of the epoxy resin of Claim 1 or 2.   The epoxy resin according to claim 3, which has a softening point of 50 to 110 ° C.   An epoxy resin composition comprising the epoxy resin according to claim 3 and a curing agent.   An epoxy resin cured product obtained by curing the epoxy resin composition according to claim 5.

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