KR101809464B1 - Polyhydroxy resin, epoxy resin, method for manufacturing the same, epoxy resin composition and cured product using the same - Google Patents

Abstract

An epoxy resin composition which is excellent in moisture resistance and heat resistance and excellent in mechanical properties such as impact resistance and is suitable for applications such as lamination, molding, casting, and bonding, and an epoxy resin and an intermediate thereof are provided.
Is an epoxy resin composition comprising a polyhydric hydroxy resin represented by the following general formula (1), an epoxy resin represented by the following general formula (2), or one or both of the polyhydric hydroxy resin and an epoxy resin as essential components. Wherein A represents a benzene ring or a naphthalene ring which may be substituted with an alkyl group having 1 to 6 carbon atoms, and G represents a glycidyl group. And n represents a number of 1 to 15.
[Chemical Formula 1]

Description

TECHNICAL FIELD The present invention relates to a polyhydroxy resin, an epoxy resin, a method for producing the same, an epoxy resin composition using the epoxy resin, and a cured product thereof. TECHNICAL FIELD [0001]

The present invention relates to an epoxy resin, an intermediate thereof, a curing agent, an epoxy resin composition using the epoxy resin, and a cured product thereof, which are excellent in flame retardancy and impart a cured product excellent in moisture resistance, heat resistance and adhesion to a metal substrate.

In recent years, development of a higher-performance base resin has been required, particularly with advances in the advanced materials field. For example, in the field of semiconductor encapsulation, the problem of package cracks becomes serious due to the thinning of the package corresponding to the recent high-density packaging, the enlargement of the package, and the spread of the surface mounting method. As the base resin, improvement in moisture resistance, heat resistance, adhesion to a metal base, and the like are strongly demanded. Further, in recent years, from the viewpoint of environmental load reduction, there has been a demand for a halogen-based flame retardant excluding agent, and a base resin having an excellent flame retardancy has been demanded.

However, it is not yet known that satisfying these demands is known to epoxy resins known from the prior art. For example, a well-known bisphenol-type epoxy resin is in a liquid phase at room temperature, is excellent in workability, and is widely used because it is easily mixed with a curing agent, an additive, etc., but has problems in terms of heat resistance and moisture resistance. A phenol novolak type epoxy resin which is an improvement of heat resistance is known, but there is a problem in moisture resistance and impact resistance. Patent Document 1 proposes an epoxy compound of a phenol aralkyl resin for the purpose of improving moisture resistance and impact resistance but is not sufficient in terms of heat resistance and flame retardancy.

In Patent Document 2, a naphthol aralkyl type epoxy resin having a structure in which naphthol is linked with a p-xylylene group has been proposed, but it is still insufficient in heat resistance and flame retardancy. Patent Document 3 proposes a naphthol aralkyl type epoxy resin having a structure in which naphthol is linked with a naphthylene group. However, since all of the aromatic structures are naphthalene rings, there is a problem that the viscosity and softening point increase, there was.

Japanese Patent Application Laid-Open No. 63-238122 JP-A-3-90075 Japanese Patent Application Laid-Open No. 2004-59792

Accordingly, an object of the present invention is to provide a polyfunctional epoxy resin useful as an epoxy resin and an epoxy resin curing agent which is excellent in moldability, has excellent performance in moisture resistance, heat resistance and flame retardancy, and is useful for applications such as lamination, molding, An epoxy resin composition using the same, and a cured product thereof.

That is, the present invention provides a compound represented by any one of the following formulas (1),

(N + B) is 0.2 to 0.7 (molar ratio), wherein A represents a naphthalene ring (N) or a benzene ring (B) and n represents a number of 1 to 15 A softening point of 70 to 120 ° C, and a melt viscosity of 2 to 10 Pa · s at 150 ° C.

Further, the present invention relates to a process for producing a naphthol compound represented by any of the following general formulas (2), (3) and (4), using 0.10 to 0.40 mol of naphthol per mol of the total amount of phenols and naphthols

(Wherein X represents a hydroxyl group, a halogen atom or an alkoxy group having 1 to 6 carbon atoms).

The present invention also relates to a compound represented by the following general formula (3),

(Wherein N represents a naphthalene ring (N) or a benzene ring (B), G represents a glycidyl group, and n represents a number of 1 to 15) 0.7, a softening point of 60 to 100 캜, and a melt viscosity of 0.2 to 1.0 Pa · s at 150 캜.

The present invention also relates to a process for producing an epoxy resin represented by the general formula (3), wherein the polyhydric hydroxy resin represented by the general formula (1) is reacted with epichlorohydrin.

Furthermore, the present invention also provides an epoxy resin composition comprising at least one of the above-mentioned epoxy resin or polyhydric hydroxy resin as an essential component of an epoxy resin component or a curing agent component, and the cured product of the epoxy resin composition to be.

The cured product obtained by curing the epoxy resin composition obtained from the epoxy resin or the polyhydric hydroxy resin of the present invention is excellent in moisture resistance and heat resistance and is excellent in mechanical properties such as impact resistance and has excellent properties such as lamination, It can be suitably used for the purpose of

1 is a GPC chart of a polyhydric hydroxy resin A. Fig.
2 is a GPC chart of the polyhydric hydroxy resin B. Fig.
3 is a GPC chart of the polyhydric hydroxy resin C. Fig.
4 is a GPC chart of the polyhydric hydroxy resin D. Fig.
FIG. 5 is a GPC chart of the polyhydric hydroxy resin E. FIG.
6 is a GPC chart of the polyhydric hydroxy resin F. Fig.
Fig. 7 is a GPC chart of a polyhydric hydroxy resin G. Fig.
8 is a GPC chart of a polyhydric hydroxy resin H. Fig.
9 is a GPC chart of the epoxy resin A. Fig.
10 is a GPC chart of the epoxy resin B. Fig.
11 is a GPC chart of the epoxy resin C;
12 is a GPC chart of the epoxy resin D. Fig.
13 is a GPC chart of the epoxy resin E. Fig.

Hereinafter, the present invention will be described in detail.

The polyhydric hydroxy resin of the present invention is represented by the above general formula (1). A represents a naphthalene ring or a benzene ring and has a structure in which a naphthalene ring (N) and a benzene ring (B) coexist and a ratio (molar ratio) of naphthalene ring (N) B) is in the range of 0.2 to 0.7. If it is smaller, the effect of improving the heat resistance and moisture resistance based on the naphthalene structure is small, and if it is larger than the above range, the softening point and the viscosity are increased, and the moldability is lowered. Here, the molar ratio is the average molar ratio of the naphthalene ring to the benzene ring in the polyhydric hydroxy resin.

The naphthalene ring and the benzene ring may be substituted with an alkyl group having 1 to 6 carbon atoms, preferably unsubstituted or substituted with a methyl group. n represents the number of repetitions of the average (number average), is 1 to 15, preferably 1.1 to 5. [ It is not preferable that n is smaller than this in terms of heat resistance. Also, in the case where the amount is larger than the above range, the softening point and the viscosity increase and the moldability decreases. The softening point of the polyhydric hydroxy resin of the present invention is in the range of 75 to 125 캜, preferably 80 to 120 캜. The melt viscosity at 150 ° C is in the range of 2 to 10 Pa · s, preferably in the range of 3 to 8 Pa · s.

Such a polyhydric hydroxy resin is obtained by reacting a phenol and a naphthol with a condensing agent represented by the general formula (2).

Here, the phenol is an alkyl group-substituted or unsubstituted phenol having 1 to 6 carbon atoms, and specific examples thereof include phenol, o-cresol, m-cresol, p-cresol, ethyl phenol, isopropyl phenol, tertiary butyl phenol, Phenol, p-phenylphenol, 2,6-xylenol, 2,6-diethylphenol and the like are exemplified. In view of low viscosity and high reactivity of the resulting resin, it is preferably an unsubstituted phenol. The naphthols are alkyl group-substituted or unsubstituted naphthols having 1 to 6 carbon atoms, preferably unsubstituted naphthols, specifically 1-naphthol and 2-naphthol. The above phenols or naphthols may be used alone or in combination of two or more.

The use ratio of the phenols and naphthols in the reaction is preferably 0.2 to 0.7 moles of the naphthol theoretical amount per mol of the total amount of both the phenols and the naphthols. When considering the difference in reactivity and the like, 0.10 to 0.40 moles of naphthol It is better to use a flow.

In the naphthalene-based condensing agent of the general formula (2), X is a hydroxyl group, a halogen atom or an alkoxy group having 1 to 6 carbon atoms. From the viewpoint of reactivity with a phenolic compound, a hydroxyl group or a halogen atom is preferable. 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 for the naphthalene ring may be the same benzene ring or different benzene ring positions. Preferred substitution positions are 1,4-position, 1,5-position, 1,6-position, 2 , 6-position, and 2,7-position. The 1,4-position and the 1,5-position are more preferable from the viewpoints of physical properties such as heat resistance, mechanical strength and toughness. The naphthalene-based condensing agent may be a mixture thereof, but it is preferable that the total content of the 1,4-di-substituted compound and the 1,5-disubstituted compound in the naphthalene-based condensing agent is 90% by weight or more.

The naphthalene-based condensation agent represented by the general formula (2) is not particularly limited, but it can be produced usually through a chloromethylation reaction of naphthalene or a chlorination reaction of a methyl group of dimethylnaphthalenes. The condensing agent may contain mono-substituted naphthalenes substituted with only one CH ₂ X group in the naphthalene ring. The content of the mono-isomer is 10 wt% or less, preferably 5 wt% or less, more preferably 3 wt% or less. If the content of the monocomponent is larger than the above value, the crosslinking density in the case of curing the resin is lowered, and the heat resistance may be lowered.

In the reaction of the phenolic compound and the naphthalene-based condensing agent, an excessive amount of phenols and naphthol are used for the naphthalene-based condensing agent. The amount of the naphthalene-based condensing agent to be used is in the range of 0.05 to 0.35 mol, preferably 0.1 to 0.3 mol, per 1 mol of the total amount of phenols and naphthols. If it is larger than the above range, the softening point of the resin tends to increase, which may hinder the molding workability. When the amount is less than this range, the amount of excess phenol and naphthol to be removed after the completion of the reaction is increased, which is industrially undesirable. Since the naphthalene-based condensing agent is used in a smaller amount than the theoretical amount, it is preferable to terminate the reaction at the time when substantially all of the naphthalene-based condensing agent is reacted.

This reaction is preferably carried out in the presence of an acid catalyst, and the acid catalyst can be appropriately selected from well-known inorganic acids and organic acids. Examples of such an acid catalyst include organic 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, Lewis acids such as iron chloride and boron trichloride, and activated clays, and solid acids such as silica-alumina and zeolite. When bischloromethylnaphthalene is used as the condensing agent represented by the general formula (2), the reaction can be carried out in the absence of a catalyst.

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

After completion of the reaction, the catalyst is removed by neutralization, water washing or the like as the case may be, and if necessary, the remaining solvent and unreacted phenolic compound are removed from the system by vacuum distillation or the like, Roxy resin. The unreacted phenolic compound is usually 3% or less, preferably 1% or less. If it is larger than the above range, the heat resistance in the case of using a cured product decreases. However, when a phenol compound having a valence of 2 or more is used in the reaction, the remaining phenolic compound may not be removed after the reaction.

In the present invention, a polyhydric hydroxy resin represented by the above general formula (1) may contain a naphthyl methane group bonded thereto. For example, when monochloromethylnaphthalene, monohydroxynaphthalene or monoalkoxymethylnaphthalene is contained in the naphthalene-based condensing agent to be reacted with the phenolic compound, the polyhydric hydroxy resin of the formula (1) 1) or a compound in which one or more naphthylmethane groups are added to the aromatic ring of the polyhydric hydroxy resin of 1). These compounds 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 is represented by the above general formula (3). Here, A and n are the same as those of the polyhydric hydroxy resin of the general formula (1). The softening point of the epoxy resin of the present invention is in the range of 60 to 100 占 폚, more preferably in the range of 75 to 95 占 폚. The melt viscosity at 150 ° C is in the range of 0.1 to 1.0 Pa · s, and more preferably in the range of 0.2 to 0.8 Pa · s.

The epoxy resin of the present invention is obtained by reacting the polyhydric hydroxy resin represented by the above general formula (1) with epichlorohydrin. This reaction can be carried out in the same manner as in the ordinary epoxidation reaction.

For example, the polyhydric hydroxy resin represented by the above-mentioned general formula (1) is dissolved in excess epichlorohydrin, and then heated in the presence of an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide at 50 to 150 ° C, And the reaction is carried out at 60 to 120 ° C for 1 to 10 hours. At this time, the amount of the alkali metal hydroxide to be used is in the range of 0.8 to 2 moles, preferably 0.9 to 1.2 moles, per 1 mole of the hydroxyl groups in the polyhydric hydroxy resin. Epichlorohydrin is used excessively with respect to the hydroxyl group in the polyhydric hydroxy resin, and is usually in the range of 1.5 to 15 mol, preferably 2 to 8 mol, per 1 mol of the hydroxyl group in the polyhydric hydroxy resin. In the reaction, a quaternary ammonium salt or the like may be added. Examples of the quaternary ammonium salt include tetramethylammonium chloride, tetrabutylammonium chloride and benzyltriethylammonium chloride. The amount of the quaternary ammonium salt to be added is preferably in the range of 0.1 to 2.0 wt% with respect to the polyhydric hydroxy resin. If the amount is less, the effect of addition of the quaternary ammonium salt is small, and if it is more than that, the amount of hydrolysable chlorine to be produced is increased, which makes it difficult to obtain high purity. A polar solvent such as dimethyl sulfoxide or diglyme may also be used, and the amount thereof to be added is preferably in the range of 10 to 200 wt% with respect to the polyhydric hydroxy resin. If it is less, the effect of addition is small, and if it is more than this amount, the volume efficiency decreases, which is not economically preferable. After completion of the reaction, the excess epichlorohydrin is removed by distillation, the residue is dissolved in a solvent such as toluene or methyl isobutyl ketone, filtered, and then washed with water to remove inorganic salts. Subsequently, the solvent is distilled off, An epoxy resin can be obtained. This epoxy resin is mainly composed of one represented by the general formula (3), and the glycidyl ether compound of the compound in which one or more naphthylmethane groups are added to the aromatic ring of the polyhydric hydroxy resin of the general formula (1) May be included. The epoxy resin of the present invention may contain an oligomerized epoxy group as an ether bond.

The epoxy resin composition of the present invention comprises an epoxy resin and a curing agent, wherein at least either one of the epoxy resins represented by the general formula (3) or the polyhydric hydroxy resin represented by the general formula (1) As an essential component. Particularly, it is preferable that an epoxy resin represented by the general formula (3) is blended as the epoxy resin component and a polyhydric hydroxy resin represented by the general formula (1) is blended as the curing agent component, since it has a high flame retardance and balance of physical properties .

As the curing agent when an epoxy resin represented by the general formula (3) is used as an essential component, any one generally known as a curing agent for an epoxy resin can be used. For example, dicyandiamide, polyhydric phenols, acid anhydrides, aromatic and aliphatic amines, and the like. Specific examples of the polyhydric phenols include bisphenol A, bisphenol F, bisphenol S, fluorene bisphenol, 4,4'-biphenol, 2,2'-biphenol, hydroquinone, resorcin, naphthalene diol (4-hydroxyphenyl) ethane, phenol novolak, o-cresol novolak, naphthol novolak, Phenol, naphthol or bisphenol A, bisphenol F, bisphenol S, fluorene bisphenol, 4,4'-biphenol, 2,2'-biphenol, hydroquinone, A polyhydric phenol compound synthesized by a condensation agent such as formaldehyde, acetaldehyde, benzaldehyde, p-hydroxybenzaldehyde, p-xylylene glycol and the like of divalent phenols such as resorcin and naphthalenediol, Phthalic anhydride, tetrahydrophthalic anhydride, methylterephthalic anhydride, La dihydro include phthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, methyl anhydride high acid anhydride, Nadic acid anhydride, trimellitic acid. Examples of the amines include 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylpropane, 4,4'-diaminodiphenylsulfone, m-phenylenediamine and p-xylylenediamine. Aromatic amines, aliphatic amines such as ethylenediamine, hexamethylenediamine, diethylenetriamine and triethylenetetramine, and polyhydric hydroxy resins represented by the general formula (1). In the resin composition of the present invention, one or more of these curing agents may be used in combination. The amount of the epoxy resin to be blended according to the present invention is in the range of 5 to 100% of the total epoxy resin.

As the epoxy resin when the polyhydric hydroxy resin represented by the general formula (1) is used as an essential component of the curing agent component, any conventional epoxy resin having two or more epoxy groups in the molecule can be used. For example, divalent phenols such as bisphenol A, bisphenol S, fluorene bisphenol, 4,4'-biphenol, 2,2'-biphenol, hydroquinone and resorcin, and tris- (4-hydroxyphenyl) Methane, 1,1,2,2-tetrakis (4-hydroxyphenyl) ethane, phenol novolak, and o-cresol novolac, or halogenated bisphenols such as tetrabromobisphenol A , Or a polyfunctional epoxy resin represented by the above general formula (1). These epoxy resins may be used alone or in combination of two or more. The blending amount of the polyhydric hydroxy resin according to the present invention is in the range of 5 to 100% of the total epoxy resin.

In the epoxy resin composition of the present invention comprising an epoxy resin represented by the general formula (3) or a polyhydric hydroxy resin represented by the general formula (1) or both as essential components, a polyester, a polyamide, a polyimide, An oligomer or a polymer compound such as a polyurethane, a petroleum resin, an indenkumarone resin, or a phenoxy resin may be appropriately blended, and an inorganic filler, a pigment, a flame retardant, a thixotropic agent, a coupling agent, Additives may be added. Examples of the inorganic filler include silica powder such as spherical or crushed fused silica and crystalline silica, alumina powder, glass powder or mica, talc, calcium carbonate, alumina, hydrated alumina and the like. Organic or inorganic extender pigments, scaly pigments, and the like. Examples of the thixotropic agent include a silicone type, a castor oil type, an aliphatic amide wax, an oxidized polyethylene wax, and an organic bentonite type. If necessary, conventionally known curing accelerators can be used. For example, amines, imidazoles, organic phosphines, and Lewis acids. The addition amount is usually in the range of 0.2 to 5 parts by weight based on 100 parts by weight of the epoxy resin. If necessary, the resin composition of the present invention may contain a releasing agent such as carnauba wax and OP wax, a coupling agent such as? -Glycidoxypropyltrimethoxysilane, a coloring agent such as carbon black, a flame retardant such as antimony trioxide, Low-stressing agents such as silicone oil, lubricants such as calcium stearate, and the like.

The cured product of the present invention can be molded by the above-mentioned epoxy resin composition by a method such as a mold, compression molding, or transfer molding. The temperature at the time of production is usually in the range of 120 to 220 占 폚.

<Examples>

Hereinafter, the present invention will be described in detail based on examples and comparative examples.

(Example 1) (Preparation of polyhydric hydroxy resin)

To a 1 L four-necked separable flask was added a mixture of 96 g of 1-naphthol, 251 g of phenol, 150 g of dichloromethylnaphthalene (1, 4-dichloromethyl compound 43.5%, 1,5-dichloromethyl compound 55.3%, other dichloromethyl compound 1.2% And 450 g of chlorobenzene were measured. The temperature was slowly elevated while stirring in a nitrogen gas stream, and the mixture was allowed to react at 80 DEG C for 2 hours. Thereafter, the temperature was raised to 180 ° C while distilling off chlorobenzene, and the reaction was continued for 1 hour. After the reaction, the solvent and the unreacted monomer were removed by distillation under reduced pressure to obtain 235 g of a brown resin (polyhydric hydroxy resin A). The obtained polyhydric hydroxy resin had a hydroxyl group equivalent of 230 g / eq., A softening point of 123 ° C and a melt viscosity of 9.5 Pa · s at 150 ° C. From the analysis of the recovered unreacted monomer, the ratio (molar ratio) of 1-naphthol (N) to phenol (B) absorbed in the resin was N / (N + B) = 0.57. A GPC chart is shown in Fig. Here, the melt viscosity was measured by CAP2000H manufactured by BROOKFIELD Co., Ltd., and the GPC measurement was carried out using a device: MODEL 151 (manufactured by Waters Corporation), 3 columns of TSK-GEL2000H and 1 piece of TSK-GEL4000H Using a solvent: tetrahydrofuran, flow rate: 1.0 ml / min, temperature: 38 DEG C, and detector: RI.

(Example 2) (Preparation of polyhydric hydroxy resin)

2-naphthol was used instead of 1-naphthol, and the reaction was conducted in the same manner as in Example 1 to obtain 237 g of a brown resin (polyhydric hydroxy resin B). The hydroxyl group equivalent of the obtained polyhydric hydroxy resin was 217 g / eq., And the softening point was 121 占 폚 and the melt viscosity at 150 占 폚 was 6.2 Pa · s. From the analysis of the recovered unreacted monomer, the ratio of 1-naphthol (N) and phenol (B) absorbed in the resin was N / (N + B) = 0.50. A GPC chart is shown in Fig.

(Example 3) (Preparation of polyhydric hydroxy resin)

100 g of 1-naphthol, 437 g of phenol, 180 g of dichloromethylnaphthalene (1,4-dichloromethyl compound 43.5%, 1,5-dichloromethyl compound 55.3%, and other dichloromethyl compound 1.2%) were added to a 1 L four- And 200 g of chlorobenzene were measured. The temperature was slowly elevated while stirring in a nitrogen gas stream, and the mixture was allowed to react at 80 DEG C for 2 hours. Thereafter, the temperature was raised to 180 ° C while distilling off chlorobenzene, and the reaction was continued for 1 hour. After the reaction, the solvent and unreacted monomer were removed by distillation under reduced pressure to obtain 275 g of a brown resin (polyhydric hydroxy resin C). The hydroxyl group equivalent of the obtained polyhydric hydroxy resin was 206 g / eq., And the softening point was 105 占 폚 and the melt viscosity at 150 占 폚 was 3.4 Pa 占 퐏. From the analysis of the recovered unreacted monomer, the ratio of 1-naphthol (N) and phenol (B) absorbed in the resin was N / (N + B) = 0.29. A GPC chart is shown in Fig.

(Example 4) (Preparation of polyhydric hydroxy resin)

To a 1 L four-neck separable flask was added a mixture of 46 g of 2-naphthol, 271 g of phenol, 215 g of dichloromethylnaphthalene (1,4-dichloromethyl compound 43.5%, 1,5-dichloromethyl compound 55.3%, and other dichloromethyl compound 1.2% And 300 g of chlorobenzene were measured. The temperature was gradually elevated while stirring in a nitrogen stream, and the mixture was allowed to react at 80 DEG C for 2 hours. Thereafter, the temperature was raised to 180 ° C while distilling off chlorobenzene, and the reaction was continued for 1 hour. After the reaction, the solvent and unreacted monomer were removed by distillation under reduced pressure to obtain 306 g of a brown resin (polyhydric hydroxy resin D). The obtained polyhydric hydroxy resin had a hydroxyl group equivalent of 213 g / eq., A softening point of 115 ° C and a melt viscosity of 4.9 Pa · s at 150 ° C. From the analysis of the recovered unreacted monomer, the ratio of 2-naphthol (N) and phenol (B) absorbed in the resin was N / (N + B) = 0.23. A GPC chart is shown in Fig.

(Example 5) (Preparation of polyhydric hydroxy resin)

In a 1 L four-neck separable flask, 224 g of 2-naphthol, 272 g of phenol, 100 g of dichloromethylnaphthalene (1,4-dichloromethyl compound 43.5%, 1,5-dichloromethyl compound 55.3%, and other dichloromethyl compound 1.2% And 300 g of chlorobenzene were measured. The temperature was gradually elevated while stirring in a nitrogen stream, and the mixture was allowed to react at 80 DEG C for 2 hours. Thereafter, the temperature was raised to 180 ° C while distilling off chlorobenzene, and the reaction was continued for 1 hour. After the reaction, the solvent and unreacted monomer were removed by distillation under reduced pressure to obtain 207 g of a brown resin (polyhydric hydroxy resin E). The obtained polyhydric hydroxy resin had a hydroxyl group equivalent of 220 g / eq. And a softening point of 120 占 폚 and a melt viscosity of 6.2 Pa 占 퐏 at 150 占 폚. From the analysis of the recovered unreacted monomer, the ratio of 1-naphthol (N) and phenol (B) absorbed in the resin was N / (N + B) = 0.70. A GPC chart is shown in Fig.

(Comparative Example 1) (Preparation of polyhydric hydroxy resin)

In a 1 L four-neck separable flask, 131 g of 1-naphthol, 25 g of 1-naphthol, 200 g of phenol, 131 g of dichloromethylnaphthalene (1,4-dichloromethyl compound 43.5%, 1,5-dichloromethyl compound 55.3%, and other dichloromethyl compound 1.2% And 300 g of chlorobenzene were measured. The temperature was gradually elevated while stirring in a nitrogen stream, and the mixture was allowed to react at 80 DEG C for 2 hours. Thereafter, the temperature was raised to 180 ° C while distilling off chlorobenzene, and the reaction was continued for 1 hour. After the reaction, the solvent and the unreacted monomer were removed by distillation under reduced pressure to obtain 255 g of a brown resin (polyhydric hydroxy resin F). The hydroxyl group equivalent of the obtained polyhydric hydroxy resin was 231 g / eq., And the softening point was 130 ° C and the melt viscosity at 150 ° C was 10.5 Pa · s. From the analysis of the recovered unreacted monomer, the ratio of 1-naphthol (N) and phenol (B) absorbed in the resin was N / (N + B) = 0.74. A GPC chart is shown in Fig.

(Comparative Example 2) (Preparation of polyhydric hydroxy resin)

In a 1 L four-neck separable flask, 57 g of 2-naphthol, 150 g of phenol, 180 g of dichloromethylnaphthalene (1,4-dichloromethyl compound 43.5%, 1,5-dichloromethyl compound 55.3%, and other dichloromethyl compound 1.2% And 400 g of chlorobenzene were measured. The temperature was slowly elevated while stirring in a nitrogen gas stream, and the mixture was allowed to react at 80 DEG C for 2 hours. Thereafter, the temperature was raised to 180 ° C while distilling off chlorobenzene, and the reaction was continued for 1 hour. After the reaction, the solvent and unreacted monomer were removed by distillation under reduced pressure to obtain 261 g of a brown resin (polyhydric hydroxy resin G). The obtained polyhydric hydroxy resin had a hydroxyl group equivalent of 234 g / eq., A softening point of 135 ° C and a melt viscosity of 14.8 Pa · s at 150 ° C. From the analysis of the recovered unreacted monomer, the ratio of 2-naphthol (N) and phenol (B) absorbed in the resin was N / (N + B) = 0.29. A GPC chart is shown in Fig.

(Comparative Example 3) (Preparation of polyhydric hydroxy resin)

In a 1 L four-neck separable flask, 320 g of 2-naphthol, 100 g of dichloromethylnaphthalene (1,4-dichloromethyl compound 43.5%, 1,5-dichloromethyl compound 55.3%, other dichloromethyl compound 1.2% And the temperature was gradually elevated while stirring in a nitrogen stream, and the mixture was allowed to react at 95 DEG C for 2 hours. Thereafter, the temperature was raised to 180 ° C while distilling off chlorobenzene, and the reaction was continued for 1 hour. After the reaction, the solvent and unreacted monomer were removed by distillation under reduced pressure to obtain 171 g of a brown resin (polyhydric hydroxy resin H). The obtained polyhydric hydroxy resin had a hydroxyl group equivalent of 253 g / eq., A softening point of 174 캜, and a melt viscosity of 150 Pa · s or more at 150 캜. The ratio of 1-naphthol (N) and phenol (B) absorbed in the resin was N / (N + B) = 1.00. A GPC chart is shown in Fig.

(Example 6)

100 g of the polyhydric hydroxy resin B obtained in Example 2 was dissolved in 298 g of epichlorohydrin and 45 g of diglyme, and 38 g of a 48% aqueous solution of sodium hydroxide was added dropwise under reduced pressure (about 120 mmHg) at 60 캜 over 4 hours. The water thus produced was removed from the system by azeotropy with epichlorohydrin, and the epichlorohydrin distilled out was returned to the system. After completion of the dropwise addition, the reaction was further continued for 1 hour. Then, epichlorohydrin and diglyme were distilled off under reduced pressure, dissolved in 295 g of methyl isobutyl ketone, and then the salt formed by washing with water was removed. Thereafter, 9 g of a 48% sodium hydroxide aqueous solution was added, and the reaction was carried out at 80 DEG C for 2 hours. After the reaction, the reaction product was washed with water and then methyl isobutyl ketone as a solvent was distilled off under reduced pressure to obtain 121 g of a brown epoxy resin (epoxy resin A). The obtained epoxy resin A had an epoxy equivalent of 268 g / eq., A softening point of 87 캜, a hydrolyzable chlorine of 120 ppm, and a melt viscosity at 150 캜 of 0.40 Pa · s. A GPC chart is shown in Fig. Here, the hydrolyzable chlorine was obtained by subjecting 0.5 g of the resin sample to 30 ml of 1N-KOH / methanol solution in which 30 ml of 1N-KOH / methanol solution was refluxed by potentiometric titration with silver nitrate solution.

(Example 7)

100 g of the polyhydric hydroxy resin D obtained in Example 4 was dissolved in 307 g of epichlorohydrin and 48 g of diglyme and reacted in the same manner as in Example 6 using 40 g of a 48% aqueous solution of sodium hydroxide to obtain 114 g of a brown epoxy resin (Epoxy resin B). The obtained epoxy resin B had an epoxy equivalent of 261 g / eq., A softening point of 84 캜, a hydrolyzable chlorine of 200 ppm and a melt viscosity at 150 캜 of 0.4 Pa · s. A GPC chart is shown in Fig.

(Example 8)

100 g of the polyhydric hydroxy resin E obtained in Example 5 was dissolved in 300 g of epichlorohydrin and 45 g of diglyme and reacted in the same manner as in Example 4 using 38.5 g of 48% aqueous sodium hydroxide solution to obtain 111 g of a brown epoxy resin (Epoxy resin C). The obtained epoxy resin C had an epoxy equivalent of 262 g / eq., A softening point of 93 캜, a hydrolyzable chlorine of 180 ppm, and a melt viscosity at 150 캜 of 0.6 Pa · s. A GPC chart is shown in Fig.

(Comparative Example 4)

100 g of the polyhydric hydroxy resin F obtained in Comparative Example 1 was dissolved in 280 g of epichlorohydrin and 42 g of diglyme and the reaction was carried out in the same manner as in Example 3 using 36.1 g of a 48% aqueous solution of sodium hydroxide to obtain 107 g of a brown epoxy resin (Epoxy resin D). The obtained epoxy resin had an epoxy equivalent of 282 g / eq., A softening point of 102 DEG C, a hydrolyzable chlorine of 320 ppm, and a melt viscosity at 150 DEG C of 1.2 Pa · s. A GPC chart is shown in Fig.

(Comparative Example 5)

100 g of the polyhydric hydroxy resin G obtained in Comparative Example 2 was dissolved in 277 g of epichlorohydrin and 42 g of diglyme and reacted in the same manner as in Example 3 using 35.6 g of 48% sodium hydroxide aqueous solution to obtain 110 g of a brown epoxy resin (Epoxy resin E). The obtained epoxy resin had an epoxy equivalent of 285 g / eq., A softening point of 120 캜, a hydrolyzable chlorine of 290 ppm, and a melt viscosity at 150 캜 of 2.5 Pa · s. A GPC chart is shown in Fig.

(Examples 9 to 16 and Comparative Examples 5 to 9)

(Having an epoxy equivalent of 280, a softening point of 84 占 폚, a melt viscosity of 0.38 Pa 占 퐏 at 150 占 폚, and an ESN (epoxy equivalent) of 150 占 폚) synthesized in Examples 1 to 8 and Comparative Examples 1 to 5 and an epoxy resin and a 2-naphthol aralkyl type epoxy resin Epoxy resin F), 3,3 ', 5,5'-tetramethyl-4,4'-dihydroxybiphenyl epoxy resin (epoxy equivalent 195, 450 ppm hydrolyzable chlorine, Epoxy resin G), phenol aralkyl resin (OH equivalent: 162, softening point: 50 占 폚, melt viscosity: 30 mPa 占 퐏 at 150 占 폚, melting point: 11 mPa 占 퐏 at 150 占 폚; YX-4000HK, Japan Epoxy Resin; Phenol resin A), 1-naphthol aralkyl resin (OH equivalent: 208, softening point: 74 占 폚; melt viscosity: 35 mPa 占 퐏 at 150 占 폚; SN-475; Shinnetsettsu Kagaku Co., Product, polyhydric hydroxy resin I) was used, triphenylphosphine as a curing accelerator, and? -Glycidoxypropyltrimethoxysilane as a silane coupling agent were used, Indicating the formulation to produce a resin composition.

As a property measurement of the resin composition, the spiral flow was a mold for spiral flow measurement conforming to the standard (EMMI-1-66). The epoxy resin composition was injected at a spiral flow injection pressure (150 kgf / cm ² ) 3 minutes, and the flow field was investigated. The gel time was such that the epoxy resin composition was poured into a recess of a gelation tester (manufactured by Nisshin Kagaku Co., Ltd.) preliminarily heated to 175 ° C and stirred at a speed of two revolutions per second using a PTFE stirring rod , And the gelation time required until the epoxy resin composition hardened was investigated. The physical properties of the cured product were molded at 175 ° C using the epoxy resin composition, post cured at 175 ° C for 12 hours to obtain a cured product test piece, and then subjected to various physical property measurements. The glass transition point and the coefficient of thermal expansion were measured by a thermomechanical measuring apparatus at a heating rate of 7 캜 / min. In the bending test, the high-temperature bending strength at 240 ° C and the bending elastic modulus were measured by the three-point bending method. The adhesive strength was evaluated by forming a molded article of 25 mm x 12.5 mm x 0.5 mm between two 42 alloy plates at 175 deg. C by a compression molding machine, post curing at 175 deg. C for 12 hours, And the strength was evaluated. The water absorption rate is obtained by forming an original disk having a diameter of 50 mm and a thickness of 3 mm by using the present epoxy resin composition, and then post-curing and moisture-absorbing for 100 hours at 85 캜 and 85% RH. The flame retardancy was expressed by the total combustion time in the test of n = 5 by molding a test piece having a thickness of 1/16 inch and evaluating it according to the UL94V-0 standard. The results are summarized in Table 2.

Claims (7)

Phenol, naphthols selected from 1-naphthol and 2-naphthol,

(Wherein X represents a hydroxyl group, a halogen atom or an alkoxy group having 1 to 6 carbon atoms).
Based condensing agent represented by the following general formula (1),

(Wherein A represents a naphthalene ring (N) or a benzene ring (B) and n represents a number of 1.1 to 5), and the molar ratio calculated by N / (N + B) is 0.2 to 0.7 , A softening point of 105 to 125 占 폚, and a melt viscosity at 150 占 폚 of 3 to 10 Pa 占 퐏. Wherein 0.10 to 0.40 mol of naphthol is used per 1 mol of the total amount of phenols and naphthols,

(Wherein X represents a hydroxyl group, a halogen atom or an alkoxy group having 1 to 6 carbon atoms), in the presence of 0.05 to 0.35 mol of a naphthalene-based condensing agent. &Lt; / RTI &gt; 3. The method of claim 2,
Wherein the total content of 1,4-di-substituent and 1,5-di-substituent in the naphthalene-based condensing agent is 90% by weight or more. A polyurethane resin prepared by reacting the polyhydric hydroxy resin according to claim 1 with epichlorohydrin,
(3),

(Wherein A represents a naphthalene ring (N) or a benzene ring (B) and G represents a glycidyl group and n represents a number of 1.1 to 5), and is calculated as N / (N + B) Wherein the molar ratio is 0.2 to 0.7, the softening point is 80 to 100 占 폚, and the melt viscosity at 150 占 폚 is 0.4 to 1.0 Pa · s. A process for producing an epoxy resin according to claim 4, wherein the polyhydric hydroxy resin according to claim 1 is reacted with epichlorohydrin. An epoxy resin composition comprising an epoxy resin and a curing agent, the epoxy resin composition comprising at least one of the polyhydric hydroxy resin according to claim 1 or the epoxy resin according to claim 4 as an essential component. A cured product obtained by curing the epoxy resin composition according to claim 6.

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