JP5139914B2 - Polyvalent hydroxy resin, epoxy resin, production method thereof, epoxy resin composition and cured product using them - Google Patents

Description

  The present invention is an epoxy resin that gives a cured product that is excellent in flame retardancy and also excellent in moisture resistance, heat resistance, adhesion to a metal substrate, etc., an intermediate thereof, a curing agent, and an epoxy resin composition using them It is suitable for insulating materials in the electrical and electronic fields such as printed wiring boards and semiconductor encapsulation.

  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, the well-known bisphenol type epoxy resin is in a liquid state at room temperature and is widely used because it is excellent in workability and easy to mix with a curing agent, an additive, etc. There is a problem in terms of moisture resistance. Also, phenol novolac type epoxy resins are known as improved heat resistance, but there are problems with moisture resistance and impact resistance. JP-A-63-238,122 proposes an epoxy compound of a phenol aralkyl resin for the purpose of improving moisture resistance and impact resistance, but it is not sufficient in terms of heat resistance and flame retardancy.

  JP-A-9-235449, JP-A-10-182792 and the like disclose a method for adding a phosphate ester-based flame retardant as a measure for improving flame retardancy without using a halogen-based flame retardant. Has been. However, the method using a phosphate ester flame retardant does not have sufficient moisture resistance. In addition, the phosphoric acid ester is hydrolyzed under a high temperature and humidity environment, and there is a problem that the reliability as an insulating material is lowered.

  Japanese Patent Application Laid-Open No. 11-140166 proposes an example in which an aralkyl epoxy resin having a biphenyl structure is applied to a semiconductor sealing material as one that improves flame retardancy without containing phosphorus atoms and halogen atoms. However, it is not sufficient in terms of flame retardancy. Furthermore, it is still not sufficient in terms of heat resistance.

JP 63-238122 A JP 9-235449 A Japanese Patent Laid-Open No. 10-182792 JP-A-11-140166

  Therefore, the object of the present invention is excellent in flame retardancy, and has excellent performance in moisture resistance, heat resistance, adhesion to a metal substrate, etc., for use in lamination, molding, casting, adhesion, etc. It is an object to provide a useful epoxy resin and a polyvalent hydroxy resin useful as an epoxy resin curing agent, a production method thereof, an epoxy resin composition using them, and a cured product thereof.

（但し、Ａは炭素数１〜６のアルキル基で置換されていてもよいナフタレン環を示す。また、ｎは１〜１５の数を示し、ｍは２を示す） That is, the present invention is a novel polyvalent hydroxy resin represented by the following general formula (1).

(However, A shows the naphthalene ring which may be substituted by the C1-C6 alkyl group. Moreover, n shows the number of 1-15 and m shows 2.)

（但し、Ｘは水酸基、ハロゲン原子又は炭素数１〜６のアルコキシ基を示す）で表されるナフタレン系縮合剤を、前者１モルに対し後者０．０５〜０．９モルの割合で反応させることにより得ることができる。
The polyvalent hydroxy resin represented by the general formula (1) includes a phenolic compound, the following general formula (2),

(Wherein X represents a hydroxyl group, a halogen atom, or an alkoxy group having 1 to 6 carbon atoms) is reacted with a 0.05 to 0.9 mole of the latter with respect to 1 mole of the former. Can be obtained.

（但し、Ａは炭素数１〜６のアルキル基で置換されていてもよいナフタレン環を示し、Ｇはグリシジル基を示す。また、ｎは１〜１５の数を示し、ｍは２を示す。） Furthermore, this invention is a novel epoxy resin represented by following General formula (3).

(However, A shows the naphthalene ring which may be substituted by the C1-C6 alkyl group, G shows a glycidyl group. Moreover, n shows the number of 1-15, m shows 2. )

  Furthermore, this invention is a manufacturing method of the novel epoxy resin represented by the said General formula (3) characterized by making the polyhydric hydroxy resin represented by the said General formula (1) react with epichlorohydrin.

  Furthermore, the present invention is an epoxy resin composition comprising at least one of the above-described epoxy resin or polyvalent hydroxy resin as an essential component of the epoxy resin component or the curing agent component, and the epoxy resin. A cured product obtained by curing the composition.

  A cured product obtained by curing an epoxy resin composition obtained from the epoxy resin or polyvalent hydroxy resin of the present invention has excellent moisture resistance, heat resistance, and excellent mechanical properties such as impact resistance. And can be suitably used for applications such as lamination, molding, casting, and adhesion.

  The polyvalent hydroxy resin of the present invention is represented by the general formula (1). Here, A represents a benzene ring or a naphthalene ring, and these rings may be substituted with an alkyl group having 1 to 6 carbon atoms, but are preferably unsubstituted or substituted with a methyl group. It is. m is 2. n represents the average number of repetitions, and is 1 to 15, preferably 1.1 to 5. Such a polyvalent hydroxy resin is obtained by reacting a phenolic compound with a condensing agent represented by the general formula (2).

  Here, the phenolic compound is an alkyl group-substituted or unsubstituted monovalent, divalent or trivalent phenol or hydroxynaphthalene having 1 to 6 carbon atoms, specifically phenol, o-cresol, m -Cresol, p-cresol, ethylphenols, isopropylphenols, tertiary butylphenols, phenylphenols, 2,6-xylenol, 2,6-diethylphenol, hydroquinone, resorcin, catechol, pyrogallol, phloroglucinol, 1 -Naphthol, 2-naphthol, 1,5-naphthalenediol, 1,6-naphthalenediol, 1,7-naphthalenediol, 2,6-naphthalenediol, 2,7-naphthalenediol, 1,3,6-trihydroxy Naphthalene, 1,3,7-trihydroxyna Examples include phthalene and 2,3,6-trihydroxynaphthalene. Of these phenolic compounds, hydroxynaphthalenes are preferred from the viewpoints of heat resistance, moisture resistance and flame retardancy. Of these, 1-naphthol or 2-naphthol is particularly preferable from the viewpoint of moisture resistance and flame retardancy, and naphthalenediols are preferable from the viewpoint of heat resistance. Said phenols or naphthols may be used independently and may use 2 or more types together. In the present invention, divalent hydroxynaphthalenes are used as the phenolic compound.

Moreover, in General formula (2), X is a hydroxyl group, a halogen atom, or a C1-C6 alkoxy group. From the viewpoint of reactivity with the phenolic compound, a hydroxyl group or a halogen atom is preferred. The halogen atom is preferably a chlorine atom, and the alkoxy group is preferably a methoxy group. The substitution positions of the two CH ₂ X groups on the naphthalene ring may be on the same benzene ring or on different benzene rings, but preferred substitution positions are 1,4-position, 1,5- Position, 1,6-position, 2,6-position, 2,7-position. From the viewpoint of physical properties such as heat resistance, mechanical strength and toughness, the 1,5-position and the 2,6-position are more preferable, and from the viewpoint of flame retardancy, the 1,5-position is particularly preferable.

Although the condensing agent represented by General formula (2) is not specifically limited, Usually, it can manufacture via the chloromethylation reaction of naphthalene or the chlorination reaction of dimethylnaphthalene. The condensing agent may contain mono-substituted naphthalenes in which only one CH ₂ X group is substituted on the naphthalene ring, but the mono-body content is 10 wt% or less, preferably 5 wt% or less, more preferably Is 3 wt% or less. If the content of the mono-body is larger than this, the crosslink density when the resin is cured may be lowered, and the heat resistance may be lowered.

  In the reaction of the phenolic compound and the condensing agent, an excessive amount of the phenolic compound is used with respect to the condensing agent. The amount of the condensing agent used is in the range of 0.05 to 0.9 mol, preferably in the range of 0.1 to 0.7 mol, with respect to 1 mol of the phenolic compound. If it exceeds the above range, the softening point of the resin becomes high, which hinders the molding workability. On the other hand, if the amount is less than this, the amount of the phenolic compound used excessively after the reaction is increased, which is not industrially preferable.

  This reaction is preferably carried out in the presence of an acid catalyst, and the acid catalyst can be appropriately selected from known inorganic acids and organic acids. Examples of such an acid catalyst include mineral acids such as hydrochloric acid, sulfuric acid, and phosphoric acid, organic acids such as formic acid, oxalic acid, trifluoroacetic acid, p-toluenesulfonic acid, and diethylsulfuric acid, zinc chloride, aluminum chloride, Examples include Lewis acids such as iron chloride and boron trifluoride, and solid acids such as activated clay, silica-alumina, and zeolite. Moreover, when using bischloromethylnaphthalene as a condensing agent represented by General formula (2), it can be made to react in the absence of a catalyst.

  Usually, this reaction is performed at 10 to 250 ° C. for 1 to 20 hours. Furthermore, alcohols such as methanol, ethanol, propanol, butanol, ethylene glycol, methyl cellosolve, ethyl cellosolve, benzene, toluene, chlorobenzene, dichlorobenzene and the like can be used as the reaction solvent.

  After completion of the reaction, in some cases, the catalyst is removed by a method such as neutralization and water washing, and if necessary, the remaining solvent and unreacted phenolic compound are removed from the system by a method such as distillation under reduced pressure. Resin. The unreacted phenolic compound is usually 3% or less, preferably 1% or less. If it is more than this, the heat resistance in the case of a cured product is lowered. However, when a divalent or higher valent phenolic compound is used in the reaction, the remaining phenolic compound may not be removed after the reaction.

  In the present invention, the polyvalent hydroxy resin represented by the general formula (1) may contain a naphthylmethane group bonded thereto. For example, when monochloromethylnaphthalene, monohydroxynaphthalene or monoalkoxymethylnaphthalene is contained in the condensing agent to be reacted with the phenolic compound, the polyvalent hydroxy resin of the general formula (1) and the general formula (1) It becomes a mixture with a compound in which one or more naphthylmethane groups are added to the aromatic ring of the polyvalent hydroxy resin. For example, when two or more types of mixtures are used for the reaction as the phenolic compound, in some cases, a polyvalent hydroxy resin containing two or more types of phenolic compounds in one molecule is generated, and the general formula (1) It becomes a mixture with the novel polyvalent hydroxy resin. Even if it is a mixture, there is no hindrance to exhibiting the effect of the present invention, and these can be used as an epoxy resin curing agent, and can be used as a raw material for the epoxy resin of the present invention.

  The epoxy resin of the present invention can be obtained by reacting the polyvalent hydroxy resin represented by the general formula (1) with epichlorohydrin. This reaction can be performed in the same manner as a normal epoxidation reaction.

  For example, after the polyvalent hydroxy resin represented by the general formula (1) is dissolved in excess epichlorohydrin, it is preferably 50 to 150 ° C. in the presence of an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide. The method of making it react for 1 to 10 hours in the range of 60-120 degreeC is mentioned. Under the present circumstances, the usage-amount of an alkali metal hydroxide is 0.8-2 mol with respect to 1 mol of hydroxyl groups in polyhydric hydroxy resin, Preferably it is the range of 0.9-1.2 mol. Epichlorohydrin is used in excess with respect to the hydroxyl group in the polyvalent hydroxy resin, but is usually in the range of 1.5 to 15 mol, preferably 2 to 8 mol, with respect to 1 mol of the hydroxyl group in the polyvalent hydroxy resin. It is. Moreover, a quaternary ammonium salt etc. can be added in the case of reaction. Examples of the quaternary ammonium salt include tetramethylammonium chloride, tetrabutylammonium chloride, benzyltriethylammonium chloride, and the addition amount thereof is in the range of 0.1 to 2.0 wt% with respect to the polyvalent hydroxy resin. Is preferred. If the amount is less than this, the effect of adding a quaternary ammonium salt is small, and if the amount is more than this, the production of hardly hydrolyzable chlorine increases and it becomes difficult to achieve high purity. Furthermore, you may use polar solvents, such as a dimethyl sulfoxide and a diglyme, and the addition amount has the preferable range of 10-200 wt% with respect to polyvalent hydroxy resin. If it is less than this, the effect of addition is small, and if it is more than this, the volumetric efficiency is lowered, which is not economical. After completion of the reaction, excess epichlorohydrin is distilled off, the residue is dissolved in a solvent such as toluene or methyl isobutyl ketone, filtered, washed with water to remove inorganic salts, and then the target epoxy is distilled off. A resin can be obtained. This epoxy resin is mainly composed of the compound represented by the general formula (3), but is a compound in which one or more naphthylmethane groups are added to the aromatic ring of the novel polyvalent hydroxy resin of the general formula (1). A glycidyl etherified product may be contained. Furthermore, what the epoxy group in the epoxy resin of this invention oligomerized as an ether bond may be contained.

  The epoxy resin composition of the present invention comprises an epoxy resin and a curing agent, and an epoxy resin represented by the general formula (3) as an epoxy resin component or a polyvalent hydroxy represented by the above general formula (1) as a curing agent component. At least one of the resins is blended as an essential component.

  As the curing agent when the epoxy resin represented by the general formula (3) is an essential component, any of those generally known as curing agents for epoxy resins 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, naphthalenediol, etc. Divalent phenols, 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 or bisphenol A, bisphenol F, bisphenol S, fluorene bisphenol, 4,4'-biphenol, 2,2'-biphenol, hydro There are polyhydric phenolic compounds synthesized by a condensing agent such as formaldehyde, acetaldehyde, benzaldehyde, p-hydroxybenzaldehyde, p-xylylene glycol, etc. of divalent phenols such as non, resorcin, naphthalene diol, etc. Examples of the product 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. Examples include aliphatic amines such as ethylenediamine, hexamethylenediamine, diethylenetriamine, and triethylenetetramine, or polyvalent hydroxy resins represented by the general formula (1). In the resin composition of the present invention, one or two or more of these curing agents can be mixed and used, but the amount of the epoxy resin related to the present invention is 5 to 100% in the entire epoxy resin. It is a range.

  As the epoxy resin when the polyvalent hydroxy resin represented by the general formula (1) is an essential component of the curing agent component, all normal epoxy resins having two or more epoxy groups in the molecule can be used. Examples include divalent phenols such as bisphenol A, bisphenol S, fluorene bisphenol, 4,4′-biphenol, 2,2′-biphenol, hydroquinone, resorcin, or tris- (4-hydroxyphenyl) methane. , 1,2,2,2-tetrakis (4-hydroxyphenyl) ethane, phenol novolak, trivalent or higher phenols such as o-cresol novolak, or halogenated bisphenols such as tetrabromobisphenol A Examples thereof include glycidyl etherified products and polyfunctional epoxy resins represented by the above general formula (1). These epoxy resins can be used alone or in combination of two or more, but the blending amount of the polyvalent hydroxy resin according to the present invention is in the range of 5 to 100% in the whole epoxy resin.

  The epoxy resin represented by the general formula (3), the polyvalent hydroxy resin represented by the general formula (1), or the epoxy resin composition of the present invention containing both as essential components includes polyester, polyamide, and polyimide. , Polyethers, polyurethanes, petroleum resins, indene coumarone resins, phenoxy resins and other oligomers or polymer compounds may be blended as appropriate, inorganic fillers, pigments, refractory agents, thixotropic agents, coupling agents In addition, additives such as a fluidity improver may be blended. Examples of inorganic fillers include silica powder such as spherical or crushed fused silica and crystalline silica, alumina powder, glass powder, mica, talc, calcium carbonate, alumina, hydrated alumina, and the like, pigments As organic or inorganic extender pigments, scaly pigments, and the like. Examples of the thixotropic agent include silicon-based, castor oil-based, aliphatic amide wax, oxidized polyethylene wax, and organic bentonite-based. Furthermore, a conventionally well-known hardening accelerator can be used as needed. Examples include amines, imidazoles, organic phosphines, Lewis acids and the like. As addition amount, it is the range of 0.2-5 weight part normally with respect to 100 weight part of epoxy resins. Furthermore, if necessary, the resin composition of the present invention includes a release agent such as carnauba wax and OP wax, a coupling agent such as γ-glycidoxypropyltrimethoxysilane, a colorant such as carbon black, three A flame retardant such as antimony oxide, a low stress agent such as silicon oil, a lubricant such as calcium stearate, and the like can be used.

  The cured product of the present invention can be molded from the epoxy resin composition by a method such as casting, compression molding or transfer molding. The temperature at the time of production is usually in the range of 120 to 220 ° C.

Hereinafter, based on an Example and a comparative example, this invention is demonstrated concretely.
Example 1 (Production of polyvalent hydroxy resin)
In a 1 L 4-neck separable flask, 192 g of 1,6-naphthalenediol, dichloromethylnaphthalene (95.6% of 1,5-dichloromethyl, 3.0% of other dichloromethyl, 1.4% of monochloromethyl) ) 81 g and 550 g of toluene were weighed and gradually dissolved by heating while stirring under a nitrogen stream, and reacted for 2 hours while refluxing at about 116 ° C. Then, it heated up to 180 degreeC, distilling toluene, and was made to react as it was for 1 hour. After the reaction, the solvent was removed by distillation under reduced pressure, and then 236 g of a brown resin was obtained (polyvalent hydroxy resin A). The obtained polyvalent hydroxy resin A has a hydroxyl group equivalent of 114 g / eq. The softening point was 102 ° C., and the melt viscosity at 150 ° C. was 2.08 Pa · s. A GPC chart is shown in FIG. 1, and an infrared absorption spectrum is shown in FIG. Here, CAP2000H manufactured by BROOKFIELD is used as the melt viscosity, and GPC measurement is performed using a device: HLC-802A (manufactured by Tosoh Corporation) and a column: TSK-GEL2000H × 3 and TSK-GEL4000H × 1 (both are Tosoh ( The product was manufactured under the conditions of solvent: tetrahydrofuran, flow rate: 1.0 ml / min, temperature: 38 ° C., detector: RI.

Reference Example 1 (Production of polyvalent hydroxy resin)
In a 1 L 4-neck separable flask, 288 g of 1-naphthol, 1,5-dichloromethylnaphthalene (95.6% of 1,5-dichloromethyl, 3.0% of other dichloromethyl, 1.4 of monochloromethyl) %) 135 g and 840 g of toluene were weighed and dissolved while gradually stirring while stirring under a nitrogen stream, and reacted at reflux at about 116 ° C. for 2 hours. Then, it heated up to 180 degreeC, distilling toluene, and was made to react as it was for 1 hour. After the reaction, unreacted 1-naphthol and the solvent were removed by distillation at 200 ° C. under reduced pressure to obtain 224 g of a brown resin (polyvalent hydroxy resin B). The obtained polyvalent hydroxy resin B has a hydroxyl group equivalent of 230 g / eq. The softening point was 137 ° C., and the melt viscosity at 180 ° C. was 1.69 Pa · s. A GPC chart is shown in FIG.

Reference Example 2 (Production of polyvalent hydroxy resin)
In a 1 L 4-neck separable flask, phenol 188 g, 1,5-dichloromethyl naphthalene (9,5.6% of 1,5-dichloromethyl, 3.0% of other dichloromethyl, 1.4% of monochloromethyl) 112.5 g and 800 g of toluene were weighed and gradually dissolved by heating while stirring under a nitrogen stream, and reacted for 2 hours while refluxing at about 116 ° C. Then, it heated up to 180 degreeC, distilling toluene, and was made to react as it was for 1 hour. After the reaction, unreacted phenol and solvent were removed by distillation under reduced pressure at 200 ° C., and 142 g of a brown resin was obtained (polyvalent hydroxy resin C). The obtained polyvalent hydroxy resin C has a hydroxyl group equivalent of 191 g / eq. It was 1.1 Pa · s at 150 ° C.

Example 2 (Production of epoxy resin)
100 g of the polyvalent hydroxy resin A obtained in Example 1 was dissolved in 812.1 g of epichlorohydrin and 162.4 g of diglyme, and 71 g of 48% aqueous sodium hydroxide solution was added dropwise at 60 ° C. over 4 hours under reduced pressure (about 100 mmHg). . 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 dropping, the reaction was continued for another hour. Thereafter, epichlorohydrin and diglyme were distilled off under reduced pressure and dissolved in 348.1 g of methyl isobutyl ketone, and then the salt produced by filtration was removed. Thereafter, 21 g of a 48% aqueous sodium hydroxide solution was added and reacted at 80 ° C. for 2 hours. After the reaction, filtration and washing with water were performed, and then methyl isobutyl ketone as a solvent was distilled off under reduced pressure to obtain 131.3 g of a brown epoxy resin (epoxy resin A). The epoxy equivalent of the obtained epoxy resin A was 175.3 g / eq. The softening point was 62 ° C., hydrolyzable chlorine was 600 ppm, and the melt viscosity at 150 ° C. was 0.12 Pa · s. A GPC chart is shown in FIG. 3, and an infrared absorption spectrum is shown in FIG. Here, the hydrolyzable chlorine is obtained by subjecting 0.5 g of a resin sample dissolved in 30 ml of 1,4-dioxane to boiling and refluxing with 5 ml of 1N KOH / methanol solution for 30 minutes, and performing potentiometric titration with a silver nitrate solution. Determined by doing.

Reference Example 3 (Production of epoxy resin)
100 g of the polyvalent hydroxy resin B obtained in Reference Example 1 was dissolved in 402.9 g of epichlorohydrin and 80.6 g of diglyme and reacted in the same manner as in Example 2 using 35.2 g of 48% aqueous sodium hydroxide solution. 116 g of resin was obtained (epoxy resin B). The epoxy equivalent of the obtained epoxy resin B was 315 g / eq. The hydrolyzable chlorine was 500 ppm, and the melt viscosity at 150 ° C. was 11.5 Pa · s. A GPC chart is shown in FIG.

Reference Example 4 (Production of epoxy resin)
100 g of the polyvalent hydroxy resin C obtained in Reference Example 2 was dissolved in 48.3 g of epichlorohydrin and 96.9 g of diglyme, and the reaction was carried out in the same manner as in Example 2 using 42.3 g of 48% aqueous sodium hydroxide solution. 123 g of resin was obtained (epoxy resin C). The epoxy equivalent of the obtained epoxy resin was 271 g / eq. The hydrolyzable chlorine was 800 ppm and the melt viscosity at 150 ° C. was 0.6 Pa · s.

Examples 3-5, Reference Examples 5-9 and Comparative Examples 1-5
Polyhydric hydroxy resin or epoxy resin synthesized in Examples 1-2 and Reference Examples 1-4, 1,6-naphthalenediol aralkyl type epoxy resin (epoxy equivalent 175, softening point 74 ° C., melt viscosity at 150 ° C. 35 Pa · s; ESN-375, manufactured by Nippon Steel Chemical Co .; epoxy resin D), 2-naphthol aralkyl type epoxy resin (epoxy equivalent 280, softening point 84 ° C., melt viscosity at 150 ° C. 0.38 Pa · s; ESN − 185, manufactured by Nippon Steel Chemical; epoxy resin E), o-cresol novolac type epoxy resin (epoxy equivalent 197, softening point 54 ° C., melt viscosity 90 ° C. at 150 ° C .; EOCN-1020, manufactured by Nippon Kayaku; epoxy Resin F), epoxidized product of 3,3 ′, 5,5′-tetramethyl-4,4′-dihydroxybiphenyl (epoxy equivalent 195, hydrolyzable) Chlorine 450 ppm, melting point 105 ° C., melt viscosity at 150 ° C. 11 mPa · s; YX-4000HK, manufactured by Japan Epoxy Resin; epoxy resin G), phenol novolak (OH equivalent 104, softening point 46 ° C., melt viscosity at 150 ° C. 20 mPa S; phenol resin D) and phenol aralkyl resin (OH equivalent 162, softening point 50 ° C., melt viscosity at 150 ° C. 30 mPa · s; MEH-7800-4L, manufactured by Meiwa Kasei; phenol resin E), 1-naphthol aralkyl Resin (OH equivalent 208, softening point 74 ° C., melt viscosity 35 mPa · s at 150 ° C .; SN-475, manufactured by Nippon Steel Chemical Co., Ltd .; phenol resin F) is used as a curing accelerator, triphenylphosphine, silane coupling agent As shown in Tables 1 and 2, using γ-glycidoxypropyltrimethoxysilane as After forming into a resin composition, it was molded (150 ° C., 3 minutes) to obtain a cured test piece. The test piece was post-cured at 180 ° C. for 12 hours and then subjected to various physical property tests. The results are shown in Tables 3-4.

  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 degrees 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 240 ° C. The adhesive strength was 25 mm × 12.5 mm × 0.5 mm between two 42 alloy 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 under the conditions of 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. Flame retardancy was measured by molding a 1/16 inch thick test piece, evaluated according to UL94V-0 standard, and expressed as the total burning time in a test with n = 5. The results are summarized in Tables 3-4.

GPC chart of hydroxy compound A IR spectrum of hydroxy compound A GPC chart of hydroxy compound B GPC chart of epoxy resin A IR spectrum of epoxy resin A GPC chart of epoxy resin B

Claims (6)

The following general formula (1),

(Wherein A represents a naphthalene ring optionally substituted with an alkyl group having 1 to 6 carbon atoms, n represents a number of 1 to 15 and m represents 2). resin. The polyvalent hydroxy resin according to claim 1 , wherein n in the general formula (1) is a number of 1.1 to 5 . The following general formula (3),

(However, A shows the naphthalene ring which may be substituted by the C1-C6 alkyl group, G shows a glycidyl group, n shows the number of 1-15, m shows 2.) Epoxy resin represented by The method for producing an epoxy resin according to claim 3, wherein the polyvalent hydroxy resin according to claim 1 or 2 is reacted with epichlorohydrin. In the epoxy resin composition which consists of an epoxy resin and a hardening | curing agent, the epoxy resin composition formed by mix | blending at least any one of the polyhydric hydroxy resin of Claim 1, or the epoxy resin of Claim 3 as an essential component. Hardened | cured material formed by hardening | curing the epoxy resin composition of Claim 5.

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